Marking systems containing 3-aryl-3-heterylphthalides and 3,3-bis(heteryl)phthalides

ABSTRACT

3-Aryl-3-indolylphthalides, 3-aryl-3-pyrrolylphthalides and 3-aryl-3-carbazolylphthalides prepared by interaction of the appropriate 2-(heteroaryl)carbonylbenzoic acid and the appropriate phenylamine, and 3,3-bis(indolyl)phthalides prepared by the interaction of the appropriate 2-(indolyl)carbonylbenzoic acid and the appropriate indole are useful as color formers in pressure-sensitive carbonless duplicating systems, thermal marking systems and hectographic copying systems.

This application is a continuation-in-part of our prior copendingapplication Ser. No. 773,180, filed Mar. 1, 1977, now abandoned.

BACKGROUND OF THE INVENTION

(a) Field of the Invention

This invention relates to novel compounds classified in the field oforganic chemistry as 3-aryl-3-heteroarylphthalides and 3,3-bis(heteroaryl)phthalides useful as color precursors, particularly in theart of carbonless duplicating as, for example, in pressure-sensitivesystems, in thermal marking systems and in hectographic orspirit-reproducing copying systems; to substituted 2-(indolylcarbonyl)benzoic acids and 2-(pyrrolylcarbonyl) benzoic acids useful asintermediates to the subject phthalide color precursors; to processesfor preparing said phthalides and benzoic acids; and topressure-sensitive duplicating systems, thermal marking systems andhectographic copying systems containing the same.

(b) Description of the Prior Art

Several classes of organic compounds of widely diverse structural typesare known to be useful as colorless precursors for carbonlessduplicating systems. Among the more important classes, there may benamed phenothiazines, for example, benzoyl leuco methylene blue;phthalides with which this invention is concerned, for example, crystalviolet lactone; fluorans, for example, 2'-anilino-6'-diethylaminofluranand 2'-dibenzylamino-6'-diethylaminofluoran; and various other types ofcolorless precursors currently employed in commercially acceptedcarbonless copy systems. Typical of the many such systems taught in theprior art are those described in U.S. Pat. Nos. 2,712,507, 2,800,457 and3,041,289 which issued July 5, 1955, July 23, 1957 and June 26, 1962,respectively. Many of the color formers in the prior art suffer one ormore disadvantage such as low tinctorial strength, poor light stability,low resistance to sublimation, low susceptibility to copiability of thecolor-developed form in standard copying machines, for example, a Xeroxcopier, and low solubility in common organic solvents, the latterdisadvantage thus requiring the use of specialized and expensivesolvents in order to obtain microencapsulated solutions of sufficientconcentration for use in pressure-sensitive copying systems.

The following items to date appear to constitute the most relevant priorart with regard to the instant invention.

U.S. Pat. No. 3,491,112, issued Jan. 20, 1970 discloses in mostpertinent part of series of normally colorless phthalides stated to beuseful as color formers in pressure-sensitive copying paper which arerepresented by the structural formula ##STR1## wherein

is a heterocyclic radical selected from the group consisting of ##STR2##in which R₁ and R₂ are C₁ to C₄ alkyl, phenyl and hydrogen; Z and Y arehydrogen and dialkylamino in which alkyl is C₁ to C₄ alkyl with theproviso that only one Z and Y can be said dialkylamino while the otheris hydrogen; and R₃ and R₄ are C₁ to C₄ alkyl.

U.S. Pat. No. 3,779,753, issued Dec. 18, 1973 discloses the phthalidehaving the formula ##STR3## which is stated to be useful as an opticalfilter agent in photographic processes to protect a selectively exposedphotosensitive material from further exposure during processing in thepresence of incident light.

British Patent Specification No. 1,427,318, published Mar. 10, 1976,discloses the interaction of trimellitic anhydride andm-diethylaminophenol to obtain a mixture of4-diethylamino-2-hydroxybenzophenone-2', 4' -dicarboxylic acid and thecorresponding 2', 5'-dicarboxylic acid isomer. The isomeric mixture isthen interacted with 3,5-dimethylphenol in the presence of sulfuric acidfollowed by treatment with sodium hydroxide to obtain the compoundhaving the structure ##STR4## which is stated to be useful as a colorformer in a spirit reproducing process.

U.S. Pat. No. 3,509,174, issued Apr. 28, 1970, discloses1,2-dimethyl-3-(2-carboxybenzoyl)indole which is stated to be anintermediate to a series of 3,3-bis (3-indolyl)phthalides useful ascolor formers in pressure-sensitive copying paper.

SUMMARY OF THE INVENTION

The present invention provides novel 3-aryl-3-heteroarylphthalidesselected from among 3-aryl-3-indolyphthalides,3-aryl-3-pyrrolylphthalides, 3-aryl-3-carbazolylphthalides and3,3-bis(heteroaryl)phthalides, particularly 3,3-bis(indolyl)-phthalideswhich are useful as color formers in pressure-sensitive duplicatingsystems, in thermal marking systems and in hectographic orspirit-reproducing systems. The compounds develop colored images of goodto excellent tinctorial strength, and have the advantages of improvedlight stability, high resistance to sublimation and enhanced solubilityin common organic solvents. Certain species are also soluble in waterand lower alcohols and are therefore of particular utility as colorformers in hectographic or spirit-reproducing copying systems. Thepresent invention also provides 2-heteroarylcarbonyl benzoic acidsuseful as intermediates to the subject phthalide color formers.

In one of its composition of matter aspects the invention relates to aseries of 3-aryl-3-heteroaryl-4-R°-5-R¹ -6-R² -7-R³ -phthalides and3,3-bis(heteroaryl)-4-R°-5-R¹ -6R² -7-R³ -phthalides which are useful ascolor formers in pressure-sensitive carbonless duplicating systems,thermal marking systems or hectographic copying systems.

In a second of its composition of matter aspects, the invention relatesto certain 2-heteroaryl-carbonyl-3-R°-4-R¹ -5-R² -6-R³ -benzoic acidswhich are useful as intermediates for the preparation of the phthalidefinal products of the invention.

In one of its process aspects, the invention relates to a process forpreparing a 3-X-3-Z-4-R°-5-R¹ -6-R² -7-R³ -phthalide which comprisesinteracting a 2-(X-carbonyl) -3-R°-4-R¹ -5-R² -6-R³ -benzoic acid with a3-R⁴ -N,N-(R)₂ -aniline or a 1--R^(6') -2-R^(5') -5/6-Y^(1') -indole.

In a second process aspect, the invention relates to a process forpreparing a 3-X-3-Z-5/6-aminophthalide which comprises reducing thecorresponding 3-X-3-Z-5/6-nitrophthalide.

In a third process aspect, the invention relates to a process forpreparing a 3-X-3-Z-5/6-acetamidophthalide which comprises interactingthe appropriate 2-(X-carbonyl)-5/6-aminobenzoic acid with a 3-R⁴-N,N-(R)₂ -aniline or a 1-R^(6') -2-R^(5') -5/6-Y^(1') -indole in thepresence of acetic anhydride.

In a fourth process aspect, the invention relates to a process forpreparing a 3-X-3-Z-5/6-COOY-phthalide which comprises esterifying thecorresponding 3-X-3-Z-5/6 carboxyphthalide with an appropriatealkylating agent in the presence of an alkali.

In a fifth process aspect, the invention relates to a process forpreparing a 3-X-3-Z-5/6-CONY'Y'-phthalide which comprises amidating thecorresponding 3-X-3-Z-5/6-carboxyphthalide with the appropriate compoundof the formula HNY'Y".

In a sixth process aspect, the invention relates to a process forpreparing a 3-[(1-R⁶ -2-R⁵ -5/6-Y¹ ) -3-indolyl]-3-[(1-R^(6') -2-R^(5')-5/6-Y^(1'))-3-indolyl]-4-R°-5-R¹ -6-R² -7-R³ -phthalide in which R⁵=R^(5'), R⁶ =R^(6') and Y¹ =Y^(1') which comprises interacting a3-R°-4-R¹ -5-R² -6-R³ -phthalic anhydride with approximately twomolecular proportions of a 1-R⁶ -2-R⁵ -5/6-Y¹ -indole.

In a seventh process aspect, the invention relates to a process forpreparing a 2-(X-carbonyl)-3-R°-4-R¹ -5-R² -6-R³ benzoic acid whichcomprises interacting a 3-R°-4-R¹ -5-R² -6-R³ -phthalic anhydride with a1-R⁶ -2-R⁵ -5/6-Y¹ -indole or a 1-R⁷ -pyrrole.

In an eighth process aspect, the invention relates to a process forpreparing a 2-(X-carbonyl)-5/6-aminobenzoic acid which comprisesreducing the corresponding 2-(X-carbonyl)-5/6-nitrobenzoic acid.

The present invention provides as articles of manufacturepressure-sensitive carbonless duplicating systems, thermal markingsystems and hectographic copying systems each containing a color-formingsubstance comprising a 3-aryl-3-heteroaryl-4-R°-5-R¹ -6-R² -7-R³-phthalide or a 3,3-bis (heteroaryl)-4-R°-5-R¹ -6-R² -7-R³ -phthalide.

DETAILED DESCRIPTION INCLUSIVE OF THE PREFERRED EMBODIMENTS

More specifically, this invention, in one of its composition of matteraspects relating to the final products, resides in the novel phthalides,which are particularly useful as colorless precursors in the art ofcarbonless duplicating, thermal marking and hectograph duplicating, andwhich are selected from the group consisting of 3-X-3-Z-4-R°-5-R¹ -6-R²-7-R³ -phthalides having the formula ##STR5## wherein R°, R¹, R² and R³each represent hydrogen or halo or when R°, R³ and one of R¹ and R² areeach hydrogen, the other of R¹ and R² represents nitro, amino,acetamido, dialkylamino wherein alkyl is non-tertiary C₁ to C₄ alkyl or##STR6## in which B represents -OY or ##STR7## wherein Y is hydrogen, analkali metal cation, an ammonium cation, a C₁ to C₁₈ mono-, di- ortrialkylammonium cation, C₂ to C₁₈ alkyl, C₂ to C₁₈ alkenyl, benzyl orbenzyl substituted in the benzene ring thereof by C₁ to C₁₂ alkyl, haloor C₁ to C₈ alkoxy; Y' is hydrogen or C₁ to C₁₈ alkyl; Y" is hydrogen,C₁ to C₁₈ alkyl or C₄ to C₁₂ N,N-dialkylaminoalkyl; X represents amonovalent moiety selected from the class having the formulas ##STR8## Zrepresents a monovalent moiety selected from the class having theformulas ##STR9## where, in the above, R represents non-tertiary C₁ toC₄ alkyl, benzyl or benzyl substituted in the benzene ring by one or twoof halo or C₁ to C₃ alkyl, R⁴ represents acetamido, dialkylamino inwhich alkyl is non-tertiary C₁ to C₄ alkyl, and when one of R¹ or R²represents any of said carboxy or said carbonyl substituents, R⁴ furtherrepresents hydrogen, C₁ to C₃ alkyl, C₁ to C₄ alkoxy or halo, R⁵ andR^(5') represent hydrogen, C₁ to C₃ alkyl or phenyl, R⁶ representhydrogen, C₁ to C₁₈ alkyl, C₂ to C₄ alkenyl, benzyl or benzylsubstituted in the benzene ring by one of two of halo or C₁ to C₃ alkyl,R⁷ and R⁸ represent hydrogen, C₁ to C₃ alkyl or phenyl, and Y¹ representone or two of hydrogen, C₁ to C₃ alkyl, C₁ to C₃ alkoxy, halo or nitrowith the provisos (i) that X and Z can both simultaneously representmonovalent indolyl moieties only when at least one of R¹ and R²represent said ##STR10## (ii) X represents a pyrrolyl or a carbazolylmoiety only when Z represents a 2-R⁴ -4-N(R)₂ -phenyl moiety.

In a first particular embodiment in accordance with its final productcomposition of matter aspect, the invention sought to be patentedresides in the novel 3-[2-R⁴ -N(R)₂ -phenyl]-3-X-4-R°-5-R¹ -6-R² -7-R³-phthalides of Formula I wherein Z is 2-R⁴ -4-N(R)₂ phenyl and are ofthe formula ##STR11## wherein R, R°, R² , R³ , R⁴ and X each have thesame respective meanings given in relation to Formula I. Preferredcompounds within the ambit of this particular embodiment are: the novel3-[2-R⁴ -4-N(R)₂ -phenyl]-3-[(1-R⁶ 2-R⁵ -5/6-Y¹ ) -3-indolyl]-4-R°-5-R¹-6-R² -7-R³ -phthalides of Formula II wherein X is 1-R⁶ -2-R⁵ -5/6-Y¹-3-indolyl according to the formula ##STR12## wherein R, R°, R¹, R², R³,R⁴, R⁵, R⁶ and Y¹ each have the same respective meanings given inrelation to Formula II; the novel 3-[2-R⁴ -4-N(R)₂ -phenyl]-3-(1-R⁷-2-pyrrolyl)-4-R°-5-R¹ -6-R² -7-R³ -phthalides of Formula II wherein Xis 1-R⁷ -2-pyrrolyl according to the formula ##STR13## wherein R, R°,R¹, R²,R³, R⁴ and R⁷ each have the same respective meanings givenrelation to Formula II; and the novel 3-[2-R⁴ -4-N(R)₂ -phenyl]-3-(9-R⁸-3-carbazoyl)-4-R°-5-R¹ -6-R² -7-R³ -phthalides of Formula II wherein Xis 9-R⁸ -3-carbazolyl according to the formula ##STR14## wherein R, R°,R¹, R², R³, R⁴ and R⁸ each have the same respective meanings given inrelation to Formula II.

In a second particular embodiment in accordance with its final productcomposition of matter aspect, the invention sought to be patentedresides in the novel 3-[(1-R⁶ -2-R⁵ -5/6-Y¹ )-3-indolyl]-3-[(1-R^(6')-2-R^(5') -5/6-Y^(1') -3-indolyl]-4-R°-5-R¹ -6-R² -7-R³ -phthalides ofFormula I wherein X is 1-R⁶ -2-R⁵ -5/6-Y¹ -3-indolyl and Z is 1-R^(6')-2-R^(5') -5/6-Y^(1') -3-indolyl. Preferred compounds within the ambitof this particular embodiment are of the formula ##STR15## wherein theindolyl moieties can be the same or different; R° and R³ and at leastone of R¹ and R² represent hydrogen and the other represents ##STR16##in which B represents --OY or ##STR17## wherein Y is hydrogen, an alkalimetal cation, an ammonium cation, a C₁ to C₁₈ mono-, di- ortrialkylammonium cation, C₂ to C₁₈ alkyl, C₂ to C₁₈ alkenyl, benzyl orbenzyl substituted in the benzene ring thereof by C₁ to C₁₂ alkyl, haloor C₁ to C₈ alkoxy; Y' is hydrogen or C₁ to C₁₈ alkyl; Y" is hydrogen,C₁ to C₁₈ alkyl or C₄ to C₁₂ N,N-dialkylaminoalkyl; and R⁵, R^(5'), R⁶,R^(6'), Y¹ and Y^(1') each have the same respective meanings given inrelation to Formula I.

This invention, in a second of its composition of matter aspects,relating to intermediates, resides in the novel 2-(X-carbonyl)-3-R°-4-R¹-5R² -6-R³ -benzoic acids which are useful as intermediates to the finalproducts and having the formula ##STR18## wherein R°, R¹, R² and R³ eachrepresent hydrogen, or halo or when R°, R³ and one of R¹ and R² are eachhydrogen, the other of R¹ and R² represents amino or carboxy; Xrepresents a monovalent moiety selected from the class having theformulas ##STR19## in which R⁵ represents hydrogen, C₁ to C₃ alkyl orphenyl, R⁶ represents C₄ to C₁₈ alkyl, C₂ to C₄ alkenyl, benzyl orbenzyl substituted in the benzene ring by one or two of halo or C₁ to C₃alkyl or represents hydrogen or C₁ to C₃ alkyl only when Y¹ is otherthan hydrogen and/or when one of R¹ and R² is amino or carboxy; R⁷represents hydrogen, C₁ to C₃ alkyl or phenyl; and Y¹ represents one ortwo of hydrogen, C₁ to C₃ alkyl, C₁ to C₃ alkoxy, halo or nitro.

In a first particular embodiment in accordance with its composition ofmatter aspects relating to intermediates, the invention sought to bepatented resides in the novel 2{[(1-R⁶ -2-R⁵-5/6-Y¹)-3-indolyl]carbonyl}3-R°-4-R¹ -5-R² -6-R³ -benzoic acids ofFormula VII wherein X is 1-R⁶ -2-R⁵ -5/6-Y¹ -3-indolyl. Preferredcompounds within the ambit of this particular embodiment are of theformula ##STR20## wherein R°, R¹, R², R³, R⁵, R⁶ and Y¹ each have thesame respective meanings given in relation to Formula VII.

In a second particular embodiment in accordance with its intermediatesto final products composition of matter aspect the invention sought tobe patented resides in the novel 2-[(1-R⁷-2-pyrrolyl)carbonyl]-3-R°-4-R¹ -5-R² -6-R³ -benzoic acids of FormulaVII wherein X is 1-R⁷ -2-pyrrolyl. Preferred compounds within the ambitof this particular embodiment are of the formula ##STR21## wherein R°,R¹, R², R³ and R⁷ each have the same respective meanings given inrelation to Formula VII.

In one of its process aspects, the invention sought to be patentedresides in the process for preparing a 3-X-3-Z-4-R°-5-R¹ -6-R² -7-R³-phthalide according to Formula I which comprises interacting a2-(X-carbonyl)-3-R°-4-R¹ -5-R² -6-R³ -benzoic acid with approximatelyone molecular proportion of a 3-R⁴ -N,N-(R)₂ -aniline or a 1-R^(6')-2-R^(5') -5/6-Y^(1') -indole in the presence of an anhydride of analkanoic acid having from 2 to 5 carbon atoms wherein R°, R¹, R² and R³each represent hydrogen or halo or when R°, R³ and one of R¹ and R² areeach hydrogen, the other of R¹ and R² represents nitro, dialkylaminowherein alkyl is non-tertiary C₁ to C₄ alkyl, or carboxy; and R, R⁴,R^(5'), R^(6'), X, Y.sup. 1' and Z each have the same respectivemeanings given in relation to Formula I.

In a second of its process aspects, the invention sought to be patentedresides in the process for preparing a 3-X-3-Z-5/6-aminophthalideaccording to Formula I which comprises reducing the corresponding3-X-3-Z-5/6-nitrophthalide wherein X and Z each have the same respectivemeanings given in relation to Formula I.

In a third of its process aspects, the invention sought to be patentedresides in the process for preparing a 3-X-3-Z-5/6-acetamidophthalideaccording to Formula I which comprises interacting the appropriate3-(X-carbonyl)-5/6-aminobenzoic acid with approximately one molecularproportion of a 3-R⁴ -N,N-(R)₂ -aniline or a 1-R^(6') -2-R^(5')-5/6-Y^(1') -indole in the presence of at least two molecularproportions of acetic anhydride wherein R, R⁴, R^(5'), R^(6'), X, Y^(1')and Z each have the same respective meanings given in relation toFormula I.

In a fourth of its process aspects, the invention sought to be patentedresides in the process for preparing a 3-X-3-Z-5/6-COOY-phthalideaccording to Formula I in which Y is C₂ to C₁₈ alkyl, C₂ to C₁₈ alkenyl,benzyl or benzyl substituted in the benzene ring thereof by C₁ to C₁₂alkyl, halo or C₁ to C₈ alkoxy and X and Z have the same respectivemeanings given in relation to Formula I which comprises esterifying thecorresponding 3-X-3-Z-5/6-COOH-phthalide with an appropriate compoundselected from the group consisting of dimethyl sulfate, diethyl sulfateor Y-halogen in which Y is C₂ to C₁₈ alkyl, C₂ to C₁₈ alkenyl, benzyl,or benzyl substituted in the benzene ring thereof by C₁ to C₁₂ alkyl,halo or C₁ to C₈ alkoxy in the presence of an alkali metal hydroxide orcarbonate.

In a fifth of its process aspects, the invention sought to be patentedresides in the process for preparing a 3-X-3-Z-5/6- ##STR22## -phthalideaccording to Formula I in which Y', Y", X and Z each have the samerespective meanings given in Claim 1 which comprises amidating thecorresponding 3-X-3-Z-5/6-COOH-phthalide or appropriate carboxylicfunctional derivative thereof with the appropriate compound of theformula ##STR23## in which Y' and Y" each have the same meanings givenin relation to Formula I.

In a sixth of its process aspects, the invention sought to be patentedresides in the process for preparing a 3-[(1-R⁶ -2-R⁵-5/6-Y¹)-3-indolyl]-3-[(1-R^(6') -2-R^(5')-5/6-Y^(1'))-3-indolyl]-4-R°-5-R¹ -6-R² -7-R³ -phthalide according toFormula VI in which R⁵ ═R^(5'), R⁶ ═R^(6') and Y¹ ═Y^(1') whichcomprises interacting a 3-R°-4-R¹ -5-R² -6-R³ -phthalic anhydride withapproximately two molecular proportions of a 1-R⁶ -2-R⁵ -5/6-Y¹ -indolein the presence of an anhydride of an alkanoic acid having from 2 to 5carbon atoms wherein R°, R¹, R², R³, R⁵, R⁶, R^(5'), R^(6'), Y¹ andY^(1') each have the same respective meanings given in relation toFormula VI.

In a seventh of its process aspects, the invention sought to be patentedresides in the process for preparing a 2-(X-carbonyl)-3-R°-4-R¹ -5-R²-6-R³ -benzoic acid according to Formula VII which comprises interactinga 3-R°-4-R¹ -5-R² -6-R³ -phthalic anhydride with approximately onemolecular proportion of a 1-R⁶ -2-R⁵ -5/6-Y¹ -indole or a 1-R⁷ -pyrrolein the presence of a Lewis acid wherein R°, R¹, R² and R³ each representhydrogen or halo or when R°, R³ and one of R¹ and R² are each hydrogen,the other of R¹ and R² represents carboxy and R⁵, R⁶, R⁷, X and Y¹ eachhave the same respective meanings given in relation to Formula VII.

In an eighth of its process aspects, the invention sought to be patentedresides in the process for preparing a 2-(X-carbonyl)-5/6-amino-benzoicacid according to Formula VII which comprises reducing the corresponding2-(X-carbonyl)-5/6-nitrobenzoic acid wherein X has the same meaninggiven in relation to Formula VII.

In an article-of-manufacture aspect, the invention sought to be patentedresides in a pressure-sensitive carbonless duplicating system, thermalmarking system or hectographic copy system containing as a color-formingsubstance a 3-X-3-Z-4-R°-5-R¹ -6-R² -7-R³ -phthalide according toFormula I wherein R°, R¹, R², R³, X and Z have the same respectivemeanings given in relation to Formula I.

A particular embodiment sought to be patented resides in apressure-sensitive transfer sheet, adapted for use with a receivingsheet having an electron accepting layer, comprising a support sheetcoated on one side with a layer of pressure-rupturable microcapsules,said microcapsules containing a liquid solution of a color formingsubstance comprising at least one compound having Formula I.

Another particular embodiment sought to be patented resides in a heatresponsive record material comprising a support sheet coated on one sidewith a layer containing a mixture comprising at least one color-formingcompound having Formula I and an acidic developer arranged such thatapplication of heat will produce a mark-forming reaction between thecolor-forming compound and the acidic developer.

Preferred articles within the ambit of the particular embodimentsabove-described are those wherein the color-forming component comprisesa 3-[2-R⁴ -4-N(R)₂ -phenyl]-3-[(1-R⁶ -2-R⁵ -5/6-Y¹)-3-indolyl]-4-R°-5-R¹-6-R² -7-R³ -phthalide wherein R, R°, R¹, R², R³, R⁴, R⁵, R⁶ and Y¹ havethe same respective meanings given in relation to Formula III or a3-[(1-R⁶ -2-R⁵ -5/6-Y¹)-3-indolyl]-3-[(1-R^(6') -2-R^(5')-5/6-Y^(1'))-3-indolyl]-4-R°-5-R¹ -6-R² -7-R³ -phthalide wherein R°, R¹,R², R³, R⁵, R⁶, R^(5'), R^(6'), Y¹ and Y^(1') have the same respectivemeanings given in relation to Formula VI.

A further particular embodiment sought to be patented resides in ahectographic or spirit reproducing copying system comprising a transfersheet coated on one side with a layer containing a color-formingsubstance comprising a compound according to Formula I wherein R°, R³and one of R¹ and R² are each hydrogen, the other of R¹ and R²represents ##STR24## wherein Y is hydrogen, an alkali metal cation, anammonium cation or a C₁ to C₁₈ mono-, di- or trialkylammonium cation.

As used herein the term "halo" includes chloro, fluoro, bromo and iodo.Chloro is the preferred halo substituent because of the relatively lowcost and ease of preparation of the required chloro-substitutedintermediates and because the other halogens offer no particularadvantages over chloro. However the other above-named halo substituentsare also satisfactory.

The terms "C₁ to C₄ alkoxy" and "dialkylamino in which alkyl isnon-tertiary C₁ to C₄ alkyl" denote saturated, acyclic groups which maybe straight or branched as exemplified by methoxy, ethoxy, propoxy,isopropoxy, butoxy, sec-butoxy, isobutoxy, tert-butoxy, dimethylamino,diethylamino, ethylmethylamino, dipropylamino, dibutylamino,isobutylmethylamino, and the like.

As used herein the terms "C₁ to C₃ alkyl", "C₁ to C₁₂ alkyl" and "C₁ toC₁₈ alkyl" denote saturated monovalent straight or branched aliphatichydrocarbon radicals including methyl, ethyl, propyl, isopropyl, butyl,isobutyl, tert-butyl, amyl, 1-methylbutyl, 3-methylbutyl, hexyl,isohexyl, heptyl, isoheptyl, octyl, isooctyl, 2-ethylhexyl, nonyl,3-ethylheptyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl,n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl,1,3,5-trimethylhexyl, 1,5-dimethyl-4-ethylhexyl, 5-methyl-2-butyl-hexyl,2-propylnonyl, 2-butyloctyl, 2-pentylnonyl, 1,2-dimethylhexadecyl, andthe like.

As used herein the term "alkali metal cation" includes lithium, sodiumand potassium cations.

The term "C₁ to C₁₈ alkylammonium cation" includes ammonium cationssubstituted by from 1 to 3 alkyl groups as above described. The alkylgroups can be the same or different provided the ammonium cationcontains no more than 18 carbon atoms. As examples there can be namedmethylammonium, t-butylammonium, t-octylammonium, n-dodecylammonium,n-octadecylammonium, di-n-butylammonium, di-n-nonylammonium,isopropyl-n-butylammonium, dimethyl-n-butylammonium, triethylammonium,N-ethyl-N,N-diisopropylammonium, tributylammonium,di-n-butyl-n-octylammonium and the like.

The terms "C₁ to C_(8") alkoxy and "C₁ to C₁₈ alkoxy" includessaturated, acyclic, straight or branch-chained groups such as methoxy,ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy, tert-butoxy,n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy,n-decyloxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy,n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy,1-methylpentyloxy, 2,2-dimethyl-butyloxy, 2-methylhexyloxy,1,4-dimethylpentyloxy, 3-ethylpentyloxy, 2-methylheptyloxy,1-ethylhexyloxy, 2-propylpentyloxy, 2-methyl-3-ethylpentyloxy,1,3,5-trimethylhexyloxy, 1,5-dimethyl-4-ethylhexyloxy,5-methyl-2-butylhexyloxy, 2-propylnonyloxy, 2-butyloctyloxy,1,1-dimethylundecyloxy, 2-pentylnonyloxy, 1,2-dimethyltetradecyloxy,1,1-dimethylpentadecyloxy and the like.

The term "C₄ to C₁₂ N, N-dialkylaminoalkyl" includes branched andstraight chain alkyl groups which can be the same or different providedthe total number of carbon atoms is not less than four nor more thantwelve. As examples there can be named 2-dimethylaminoethyl,diethylaminomethyl, 3-dimethylaminopropyl, 1-dimethylamino-2-propyl,3-diethylaminopropyl, 1-diethylamino-2-propyl, 2-dipropylaminoethyl,2-di-i-propylaminoethyl, 3-dipropyl-aminopropyl, 3-dimethylaminopropyl,4-diethylamino-n-butyl, 3-di-butylaminopropyl, 4-dimethylamino-n-butyl,5-diethylaminopentyl, 5-dipropylaminopentyl, 6-dimethylamino-n-hexyl,6-diethylamino-6-ethylhexyl, 4-dibutylamino-n-butyl,8-dimethylamino-n-octyl, 8-diethylamino-n-octyl,10-dimethylamino-n-decyl, 5-dipropylamino-2-pentyl and the like.

As used herein, the term "C₂ to C₁₈ alkenyl" means a monovalentaliphatic radical possessing a single double bond, for example, ethenyl(or vinyl), 2-propenyl (or allyl), 1-methyl-ethenyl (or isopropenyl),2-methyl-2-propenyl, 2-methyl-1-propenyl, 2-butenyl, 3-butenyl,1-pentenyl, 2-pentenyl, 3-methyl-2-butenyl, 2-methyl-1-butenyl(isoamylenyl), 3-methyl-1-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl,2-heptenyl, 1-octenyl, 1-hexadecenyl, 9-octadecenyl, 9-decenyl,1-methyl-4-butenyl, 4-pentenyl, 1-ethyl-1-propenyl, 1-ethyl-3-propenyl,10-undecenyl and the like.

Anhydrides of alkanoic acids of two to five carbon atoms include aceticanhydride, propionic anhydride, butyric anhydride, isobutyric anhydride,valeric anhydride, isovaleric anhydride, α-methylbutyric anhydride,pivalic anhydride and the like. Acetic anhydride is preferred because ofits low cost and high reactivity, however the other above-namedanhydrides are also satisfactory.

The novel compounds of Formula I hereinabove are essentially colorlessin the depicted form. When contacted with an acidic medium, for examplesilica gel or one of the types ordinarily employed in pressure-sensitivecarbonless duplicating systems such as silton clay or phenolic resinsthe compounds of Formula I develop an orange-red through green to ablackish-purple colored image of good to excellent tinctorial strength,and possessing excellent light stability, resistance to sublimation andxerographic copiability. The compounds are thus highly suitable for useas colorless precursors, that is color-forming substances inpressure-sensitive carbonless duplicating systems. The darker violetsand bluish-black colors can be used alone as color formers to produceimages which are readily copiable, whereas the reds, greens and bluecolors can be used as toners in admixture with other color formers toproduce images of a neutral shade which desirably are readily copiableby xerographic means. Moreover, the compounds of Formula I, inparticular those wherein one of R¹ and R² represents ##STR25## in whichB represents -OY or ##STR26## wherein Y is C₂ to C₁₈ alkyl, C₂ to C₁₈alkenyl, benzyl or benzyl substituted in the benzene ring thereof by C₁to C₁₂ alkyl, halo or C₁ to C₈ alkoxy; Y'is hydrogen or C₁ to C₁₈ alkyl;Y" is hydrogen, C₁ C₁₈ alkyl or C₄ to C₁₂ N,N-di-alkylaminoalkyl haveenhanced solubility in common and inexpensive organic solvents such asodorless mineral spirits, kerosene, vegetable oils and the like; andthose wherein one of R¹ and R² is an alkali-metal cation, an ammoniumcation or a C₁ to C₁₈ mono-, di- or trialkylammonium cation salt of thecarboxy group are soluble in water and lower-alkanols thereby avoidingthe need for more expensive, specialized solvents such aspolyhalogenated or alkylated biphenyls which have ordinarily been usedto prepare microencapsulated solutions of the color formers of the priorart.

The compounds of this invention may be incorporated in any of thecommercially accepted systems known in the carbonless duplicating art. Atypical technique for such application is as follows. Solutionscontaining one or more colorlss precursor compounds of Formula I,optionally in admixture with other color formers, in suitable solventsare microencapsulated by well-known procedures for example as describedin U.S. Pat. No. 3,649,649. The microcapsules are coated on the reverseside of a transfer sheet with the aid of a suitable binder and thecoated transfer sheet is then assembled in a manifold with themicrocapsule coated side in contact with a receiving sheet coated withan electron accepting substance, for example, silton clay or a phenolicresin. Application of pressure to the manifold such as that exerted by astylus, typewriter or other form of writing or printing causes thecapsules on the reverse side to rupture. The solution of the colorformer released from the ruptured microcapsules flows to the receivingsheet and on contact with the acidic medium thereon forms orange-red toviolet-black colored images of good tinctorial strength. It is, ofcourse, obvious that variants of this mode of application can beutilized. For example, the receiving sheet in a manifold canalternatively be coated with the subject compounds and the acidicdeveloping agent can be contained in microcapsules applied to thereverse side of the top sheet in the manifold; or the receiving sheetcan be coated with a mixture containing both the acidic developing agentand the microencapsulated color former.

It has also been found that when the compounds of Formula I areintimately mixed with an acidic developer of the type generally employedin thermal papers such as described in U.S. Pat. No. 3,539,375, that is,papers which produce a colored image when contacted with a heated stylusor heated type, for example, bisphenol A, heating of the mixtureproduces a colored image of varying shades from orange-red toviolet-black depending on the particular commpound of the inventionemployed. The ability of the compounds of Formula I to form a deep colorwhen heated in admixture with an acidic developer such as bisphenol A,makes them useful in thermal paper marking systems, either where anoriginal or a duplicate copy is prepared by contacting the thermal paperwith a heated stylus or heated type in any of the methods generallyknown in the art.

The compounds of this invention which are soluble in water andlower-alkanols may be incorporated in any of the commercial hectographicor spirit-reproducing copying systems such as described in British Pat.No. 1,427,318 published Mar. 10, 1976. In such systems a transfer sheetcoated on one side with a layer containing one or more water- or loweralkanol-soluble color formers of Formula I is placed with its coatedsurface against one surface of a master paper which is then typed,written or marked on, causing transfer of the coating as a substantiallycolorless reverse image to the master paper at the points where thetransfer sheet and master paper have been pressed together. The masterpaper is then brought into contact with a succession of sheets of papermoistened with a suitable spirit-reproducing fluid such as ethanol. Thefluid dissolves a part of the color former and transfers it to eachpaper sheet where it combines with an electron-accepting substance, togive a orangish-red to violet-black colored image which duplicates theoriginal typing or writing on the master paper.

The best mode contemplated by the inventors of carrying out thisinvention will now be described so as to enable any person skilled inthe art to which it pertains to make and use the same.

In accordance with one of the process aspects of this invention the3-X-3-Z-4-R°-5-R¹ -6-R² -7-R³ -phthalides of Formula I wherein R⁰, R¹,R² and R³ each represent hydrogen or halo or when R°, R³ and one of R¹and R² are each hydrogen and the other represents nitro, dialkylamino orcarboxy are obtained by interacting approximately an equimolar quantityof the appropriate 2-(X-carbonyl)-3-R°-4-R¹ -5-R² -6-R³ -benzoic acidwith the appropriate 3-R⁴ -N,N-(R)₂ -aniline or a 1-R^(6') -2-R^(5')-5/6-Y^(1') -indole. The reaction is conveniently carried out in thepresence of an anhydride of an alkanoic acid having from 2 to 5 carbonatoms, for example, acetic anhydride at a temperature in the range of10° to 140° C. for from approximately thirty minutes to eighteen hours.The 3-X-3-Z-4-R°-5-R¹ -6-R² -7-R³ -phthalide thus obtained can beisolated by filtration if it is insoluble in the reaction medium or bydilution of the reaction medium with a miscible solvent in which theproduct is insoluble, for example, a lower-alkanol or low molecularweight hydrocarbon, for example, isopropyl alcohol or hexane to effectprecipitation of the phthalide. Alternatively, the reaction mixture canbe poured into an aqueous base or an aqueous base added to the reactionmixture, for example, dilute ammonium hydroxide, sodium hydroxide orsodium carbonate and the phthalide extracted with an organic solvent,for example, benzene or toluene followed by evaporation of the organicsolvent leaving the product as a residue. The phthalide once isolatedcan be purified by conventional means such as trituration orrecrystallization from a suitable solvent. In a second alternativemethod, the reaction mixture can be added to an aqueous acid, forexample, dilute hydrochloric acid and the pH adjusted by the addition ofa dilute alkali, for example, dilute aqueous ammonium hydroxide or analkaline salt, for example, sodium acetate and the product filtered orextracted as described above.

The 3-[(1-R⁶ -2-R⁵ -5/6-Y¹)-3-indolyl]-3-[(1-R^(6') -2-R^(5')-5/6-Y^(1'))-3-indolyl]-4-R°-5-R¹ -6-R² -7-R³ -phthalides of Formula VIin which the indole moieties are the same can be prepared by interactingtrimellitic anhydride with approximately two molecular proportions ofthe appropriate 1-R⁶ -2-R⁵ -5/6-Y¹ -indole. The reaction is convenientlycarried out in the anhydride of an alkanoic acid having from two to fivecarbon atoms, for example acetic anhydride at a temperature in the rangeof 10° to 140° C., but more desirably, at a temperature in the range of75° to 140° C. to obtain the desired 3-[(1-R⁶ -2-R⁵-5/6-Y¹)-3-indolyl]-3-[(1-R^(6') -2-R^(5')-5/6-Y^(1'))-3-indolyl]-5/6-carboxyphthalide. The phthalides areisolated in a manner similar to that indicated in the first mode ofsynthesis described above.

In accordance with a further process aspect of the present invention the3-X-3-Z-5/6-aminophthalides of Formula I can be prepared by reducing thecorresponding 3-X-3-Z-5/6-nitrophthalide. The reduction is convenientlycarried out in an acidic medium, for example, hydrochloric acid using ametal salt reducing agent, for example, stannous chloride at atemperature in the range of 0° to 80° C., but more desirably, at atemperature in the range of 50°-80° C. The desired phthalide iscollected by filtration and purified by conventional means for examplerecrystallization from a suitable solvent after an aqueous alkaliextraction.

In accordance with a fourth of the process aspects of this invention,the 3-X-3-Z-5/6-acetamidophthalide according to Formula I can beconveniently obtained by interacting the appropriate3-(X-carbonyl)-5/6-aminobenzoic acid with approximately an equimolarquantity of an appropriate 3-R⁴ -N,N-(R)₂ -aniline or a 1-R^(6')-2-R^(5') -5/6-Y^(1') -indole in the presence of at least two molecularproportions of acetic anhydride. The product is isolated by adding waterand dilute alkali to the reaction mixture and the product extracted withan organic solvent, for example, benzene or toluene followed byevaporation of the organic solvent leaving the phthalide as acrystalline material.

The 3-X-3-Z-5/6-COOY-phthalides of Formula I in which Y is C₂ to C₁₈alkyl, a C₂ to C₁₈ alkenyl, a benzyl or a benzyl substituted in thebenzene ring thereof by C₁ to C₁₂ alkyl, halo or C₁ to C₈ alkoxy areobtained by interacting a 3-X-3-Z-5/6-COOH-phthalide with an appropriatealkylating agent, for example, dimethyl sulfate, diethyl sulfate, ethyliodide, butyl bromide, allyl chloride, octyl bromide, hexadecyl bromideor benzyl bromide in an inert diluent, for example, acetone,N,N-dimethylformamide or hexamethylphosphoramide in the presence of analkali metal salt, for example, sodium hydroxide, sodium carbonate,potassium hydroxide or potassium carbonate. The reaction is convenientlycarried out at a temperature in the range of 10° to 100° C. forapproximately one to three hours. The 3-X-3-Z-5/6-COOY-phthalide thusobtained is isolated by adding the reaction mixture to water withsubsequent extraction into and subsequent isolation from an aromaticsolvent, for example, benzene or toluene. The organic layer isseparated, dried over a suitable drying agent, followed by evaporationof the organic solvent leaving the phthalide as a residue. The productonce isolated can be purified by conventional means such as triturationor recrystallization from a suitable solvent.

In accordance with another process aspect of this invention the3-X-3-Z-5/6-CONY'Y"-phthalides of Formula I are obtained by amidatingthe corresponding 3-X-3-Z-5/6-COOH-phthalide or the appropriatecorresponding 3-X-3-Z-5/6-COOY-phthalide with the appropriate Y'Y"NHamine, for example, 3-(di-n-butylamino)-propylamine. The reaction isconveniently carried out optionally in the presence of an inert diluentor in the absence of an inert diluent at a temperature in the range of90° to 150° C. for approximately five hours. The phthalide thus obtainedcan be isolated by adding the reaction mixture to water and the productextracted with an organic solvent, for example, benzene or toluene. Theorganic layer is separated and evaporated or distilled in vacuum toleave the product as a residue or oil.

The 3-X-3-Z-5/6-COOY-phthalides wherein the Y is an alkali metal cation,an ammonium cation or a mono-, di- or tri-alkylammonium cation areobtained by interacting the appropriate 3-X-3-Z-5/6-COOH-phthalide withapproximately an equimolar quantity of an appropriate alkali metal salt,for example, sodium hydroxide, potassium hydroxide or lithium hydroxide,ammonium hydroxide or an amine, for example,1,1,3,3-tetramethylbutylamine. The reaction is conveniently carried outin an inert diluent, for example, acetone at a temperature in the rangeof 10° to 50° C. for approximately five minutes to one hour. Thephthalide thus obtained is isolated by dilution of the reaction mediumwith a miscible solvent in which the product is insoluble, for example,low molecular weight hydrocarbons such as hexane in order to effectprecipitation of the product. The phthalide once isolated can bepurified by conventional means such as trituration or recrystallizationfrom a suitable solvent.

Both the known and the novel 2-X-carbonyl-3-R°-4-R¹ -5-R² -6-R³ -benzoicacids of Formula VII are prepared in similar fashion, by interacting a3-R°-4-R¹ -5-R² -6-R³ -phthalic anhydride with a 1-R⁶ -2-R⁵ -5/6-Y¹-indole, a 1-R⁷ -pyrrole, or a 9-R⁸ -carbazole wherein R°, R¹, R², R³,R⁵, R⁶, R⁷, R⁸ and Y¹ each have the same meanings given in relation toFormula I usually in the presence of a Lewis acid, for example, aluminumchloride or zinc chloride, and with a diluent such as benzene, toluene,xylene, chlorobenzene, 1,2-dichloroethane or o-dichlorobenzene at atemperature of about 0° to 150° C. The reaction is conveniently carriedout in toluene in the presence of aluminum chloride at about 0° to 25°C. Alternatively, the more reactive indoles can be interacted in theabsence of a Lewis acid by simply heating the reactants together in aninert solvent at about 80° to 150° C. The 2-(X-carbonyl)-3-R°-4-R¹ -5-R²-6-R³ -benzoic acids in which Lewis acids are used in their preparationare isolated by adding water to the reaction mixture or the reactionmixture to water or dilute mineral acid, for example, hydrochloric acidand subsequently separating the organic layer. The product is extractedfrom the organic layer with a dilute aqueous alkali solution andprecipitated by the addition of a mineral acid, for example,hydrochloric acid. The benzoic acid is collected by filtration and maybe purified by conventional means but is generally dried and used as is.Alternatively, in the case where the more reactive indoles are utilized,it is preferable not to use a Lewis acid and the2-(X-carbonyl)-3-R°-4-R¹ -5-R² -6-R³ -benzoic acids are obtained bycooling the reaction mixture to ambient temperature and collecting theproduct by filtration. The product once isolated can be purified byconventional means but preferably the benzoic acid is dried and used asis.

In accordance with one of the process aspects of this invention, the2-(X-carbonyl)-5/6-aminobenzoic acids of Formula VII are obtained byreducing the corresponding 2-(X-carbonyl)-5/6-nitrobenzoic acid. Thereduction is conveniently carried out in an acidic medium, for example,hydrochloric acid using a metal salt reducing agent, for example,stannous chloride at a temperature in the range of 0° to 80° C., butpreferably at a temperature in the range of 50°-80° C. The desiredbenzoic acid is collected by filtration and purified if desired byconventional means but preferably it is dried and used as is.

It will, of course, be appreciated that reaction of an unsymmetricallysubstituted phthalic anhydride with an indole, pyrrole or carbazole canproduce isomers or a mixture of isomers of 2-(heteroarylcarbonyl)benzoicacids. For example, reaction of a 4-substituteed phthalic anhydride withan indole, pyrrole or carbazole can produce either a 4- or 5-substituted2-(heteroarylcarbonyl)benzoic acid or a mixture thereof. Similarly a3-substituted phthalic anhydride can produce either a 3- or a6-substituted 2-(heteroarylcarbonyl)benzoic acid or a mixture of these.These mixtures of isomeric 2-(heteroarylcarbonyl)benzoic acids can beseparated by conventional means such as fractional crystallization orchromatography. Alternatively, the isomeric mixtures can be reacteddirectly with appropriate 3-R⁴ -N,N-(R)₂ -anilines or 1-R^(6') -2-R^(5')-5/6-Y^(1') -indoles to produce isomeric mixtures of phthalides ofFormula I. Thus, reaction of a mixture of 4- and 5-substituted2-(heteroarylcarbonyl)benzoic acids with a 3-R⁴ -N,N-(R)₂ -aniline or a1-R^(6') -2-R^(5') -5/6Y^(1') -indole will produce a mixture of 5- and6-substituted phthalides. The mixtures of phthalides can, if desired, beseparated by conventional means or simply and preferably used asmixtures in the practice of this invention. Throughout this applicationwhere the possibility of different isomeric products being formed ispresent, the nomenclature 4/5, 5/6 and so forth is adopted meaning theproduct obtained or claimed is a mixture of the isomers.

Indole, the substituted indoles, pyrrole, the substituted pyrroles,carbazoles and the substituted carbazoles required as intermediates forthe preparation of the carbonylbenzoic acid intermediates of FormulasVII, VIII and IX and for the final products of Formulas I, II, III, IV,V and VI form an old and well-known class of compounds which are readilyobtained by conventional procedures well known in the art. The followingcompounds are exemplary of indoles, pyrroles and carbazoles useful inthe practice of this invention.

Indole,

1-Methylindole,

2-Methylindole,

1,2-Dimethylindole,

1-Ethyl-2-methylindole,

2-Phenylindole,

1-Propyl-2-methylindole,

1-Benzyl-2-methylindole,

1-Butyl-2-methylindole,

1-Octyl-2-methylindole,

2-Ethyl-5-methylindole,

1-Benzyl-5-fluoroindole,

1-Methyl-6-nitroindole,

5-Methoxy-1-butylindole,

1-Allyl-2-methylindole,

1,2-Dimethyl-6-nitroindole,

1-(4-Chlorobenzyl)-2-methyl-5-nitroindole,

2-Ethylindole,

2-Ethyl-1-methylindole,

1-Isopropylindole,

2-Isopropylindole,

1-Methyl-5-bromo-6-nitroindole,

2,5,6-Trimethylindole,

1-Isobutyl-2-methylindole,

6-Bromo-2-methylindole,

1-Hexylindole,

1-(2,5-Dimethylbenzyl)-2-methylindole,

2-Propylindole,

6-Chloro-2-phenylindole,

1-(2-Ethylhexyl)-2-methylindole,

1-(2,6-Dichlorobenzyl)-2-methylindole,

1-Vinyl-2-methylindole,

2-Ethyl-6-methylindole,

6-Fluoro-1-benzylindole,

1-(4-Bromobenzyl)-2-isopropylindole,

1-(3-Chlorobenzyl)-2-ethylindole,

5-Chloro-1-benzylindole,

1-(2-Fluorobenzyl)-2-methylindole,

5-Iodo-1-(1-methylhexyl)indole,

5,6-Dimethoxyindole,

1-(2-Methylbenzyl)-2-methylindole,

5,6-Dichloro-2-phenylindole,

1-Isoamylindole,

1-[3-(2-Methyl)-1-propenyl]-2-methoxyindole,

Pyrrole,

N-Methylpyrrole,

N-Ethylpyrrole,

N-Propylpyrrole,

N-Isopropylpyrrole,

N-Phenylpyrrole,

Carbazole,

9-Methylcarbazole,

9-Ethylcarbazole,

9-Propylcarbazole,

9-Isopropylcarbazole, and

9-Phenylcarbazole.

The 3-R⁴ -N,N-(R)₂ -anilines, which are required for interaction withthe 2-(X-carbonyl)-3-R°-4-R¹ -5-R² -6-R³ -benzoic acids of Formula VIIto obtain the 3-X-3-[2-R⁴ -4-N(R)₂ -phenyl]-4-R°-5-R¹ -6-R² -7-R³-phthalides of Formula II form an old and well-known class of compoundsreadily obtained by conventional procedures well known in the art. Thefollowing list of anilines exemplifies compounds falling within theambit of the formula Z-H which are useful in the practice of the step inthe processes of this invention for producing the aforesaid phthalidesof Formula II.

N,N, N',N'-Tetramethyl-m-phenylenediamine,

N,N-Dibutylaniline,

N,N-Diethyl-3-ethoxyaniline,

N,N-Diethyl-m-anisidine,

N,N-Dimethylaniline,

N-Benzyl-N-ethylaniline,

N,N-Diethyl-m-toluidine,

N,N-Diethylaniline,

N-Ethyl-N-methylaniline,

N-Benzyl-N-methylaniline,

N-Benzyl-N-propylaniline,

N,N-Dimethyl-3-bromoaniline,

N,N,N',N'-Tetraisopropyl-m-phenylenediamine,

N,N-Dibutyl-3-fluoroaniline,

N,N-Diethyl-2-methoxy-3-chloroaniline,

N-Benzyl-N-methyl-3-ethylaniline,

N,N,N',N'-Tetra-sec-butyl-m-phenylenediamine,

N-Benzyl-N-butyl-3-iodoaniline,

N,N-Diisopropyl-3-chloroaniline,

N-Benzyl-N-sec-butylaniline,

N,N-Di-sec-butylaniline,

N,N-Diethyl-3-isopropylaniline,

N,N-Diisobutylaniline,

N,N-Diethyl-2-propoxyaniline,

N,N-Dipropylaniline,

N-Isopropyl-N-methylaniline,

N-Methyl-N-propylaniline,

N,N,N',N'-Tetrabutyl-m-phenylenediamine,

N,N-Dipropyl-o-anisidine,

N-Isobutyl-N-ethylaniline,

N,N,N',N'-Tetraethyl-m-phenylenediamine,

N-Propyl-N-ethylaniline,

N,N-Diethyl-2-ethoxyaniline,

N-Benzyl-N-sec-butyl-2-propoxyaniline, and

N,N-Dimethyl-m-toludine.

The molecular structures of the compounds of this invention wereassigned on the basis of the modes of synthesis, elemental analysis andstudy of their infrared, nuclear magnetic resonance, and mass spectra.

The following examples will further illustrate the invention without,however, limiting it thereto.

EXAMPLE 1

A. To a stirred suspension of 22.5 g (0.15 mole) of phthalic anhydrideand 61.0 g (0.30 mole) of 77.5 percent active 1-ethyl-2-methylindole in120 ml of ethylene dichloride chilled to 0° to 5° C. by means of an icebath, there was added in small portions 32.0 g (0.24 mole) of aluminumchloride. The mixture was maintained at 0°-5° C. for an additional 15minutes, allowed to warm to room temperature and stirred overnight.Then, 240 ml of water was added to the reaction mixture and the ethylenedichloride layer was separated from the acidic aqueous layer. Theorganic layer was extracted with 600 ml of 3.5 percent aqueous sodiumhydroxide. The alkaline extract was acidified with dilute hydrochloricacid and the separated solid collected, washed with water and dried toobtain 24.0 g of 2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid(Formula VIII: R°═R¹ ═R² ═ R³ ═Y¹ ═H; R⁵ ═CH₃ ; R⁶ ═CH₂ CH₃), a slightlypink solid having a melting point of 184°-185° C.

B. A mixture of 12.28 g (0.04 mole) of2-[(1-ethyl-2-methyl3-indol)carbonyl]benzoic acid, prepared as describedin part A above, 10.7 g (0.043 mole) of 90 percent activeN,N,N',N'-tetraethyl-m-phenylenediamine and 6.0 ml of acetic anhydridewas stirred at room temperature for seventeen hours. The reactionmixture was diluted with 26.0 ml of ethanol, stirred and filtered. Theseparated solid was washed with diethylether and dried to yield 11.8 gof3-[2,4-bis(diethylamino)phenyl-]-3-(1-ethyl-2methyl-3-indolyl)phthalide(Formula III: R°═R¹ ═R² ═R³ ═Y¹ ═H; R═R⁶ ═CH₂ CH₃ ; R⁴ ═N(CH₂ CH₃)₂ ; R⁵═CH₃), a white crystalline material which melted at 139°-140° C. Theinfrared spectrum showed a significant band at 1760 cm⁻¹ (C═O; s) andthe nuclear magnetic resonance spectrum was in accord with thestructure. A solution of this product in benzene developed a deepblue-black color when spotted on silica gel.

C. In a procedure similar to that described above in part B of thisexample, 12.28 g (0.04 mole) of2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, prepared asdescribed in part A above, 8.57 g (0.05 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine and 6.0 ml of acetic anhydridewere interacted with stirring at room temperature overnight. Thereaction mixture was then diluted with 13.0 ml of ethanol and theprecipitate which separated was filtered and washed with 6.0 ml ofethanol. The filter cake was then reslurried in 30 ml of methanol,filtered and washed successively with methanol and diethylether. Thematerial was dried in vacuo to obtain 15.8 g of3-[2,4-bis(dimethylamino)phenyl]3-(1-ethyl-2-methyl-3-indolyl)phthalide(Formula III: R°═R¹ ═R² ═R₃ ═Y¹ ═H; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂ ; R⁶ ═CH₂CH₃), a white crystalline solid which melted at 218° -222° C. Theinfrared spectrum was consistent with the structure. A benzene solutionof the above product developed in intense grape-red color when streakedon a phenolic resin coated paper.

EXAMPLE 2

A. To a stirred suspension of 9.66 g (0.017 mole) of tetrachlorophthalicanhydride and 13.5 g (0.034 mole) of 80 percent active1-ethyl-2-methylindole in 30 ml of benzene maintained at 0°-5° C. bymeans of a ice bath, 10.6 g (0.079 mole) of aluminum chloride was addedin small increments. The reaction mixture was then maintained at 0° to5° C. for an additional twenty minutes, allowed to warm to roomtemperature and stirred overnight. The mixture was transferred to abeaker and triturated successively with hexane, 10 percent hydrochloricacid, and lastly with 5 percent aqueous sodium hydroxide which had beenheated to 70° C. The residual oil was filtered, acidified with dilutehydrochloric acid and allowed to stand overnight. On standing, the oilgave way to a solid which was collected by filtration, washed with waterand dried to yield 6.8 g of2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]3,4,5,6-tetrachlorobenzoic acid(Formula VIII: R°═R¹ ═R² ═R³ ═Cl; R⁵ ═CH₃ ; R⁶ ═CH₃ CH₂ ; Y¹ ═H), an offwhite solid melting at 214°-216° C. Analysis by mass spectrum showed m/epeaks at 443 (M⁺, Cl═35) and 398 (M³⁰ --COOH).

B. A stirred mixture of 8.86 g of2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]-3,4,5,6-tetrachlorobenzoicacid, prepared as described in part A above, 4.0 g ofN,N,N',N'-tetramethyl-m-phenylenediamine, and 10.0 ml of aceticanhydride was heated at reflux for a period of three hours. The reactionwas then allowed to cool to room temperature, and the tan precipitatewhich formed was filtered an washed with isopropanol. The material thusobtained was dissolved in 500 ml of benzene and the resulting solutionextracted with 70 ml of 10 percent aqueous sodium hydroxide. The benzenesolution was filtered and evaporated to dryness at ambient temperatureyielding 1.5 g of3-[2,4-bis(dimethylamino)-phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-4,5,6,7-tetrachlorophthalide(Formula III: R°═R¹ ═R² ═R³ ═Cl; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂ ; R⁶ ═CH₂ CH₃ ;Y¹ ═H), a white solid which melted with decomposition at 227°-229° C. Asignificant infrared maximum occurred at 1770 cm⁻¹ (C═O; s). The nuclearmagnetic resonance spectrum was in complete agreement with the assignedstructure. A benzene solution of this product spotted on silica geldeveloped an intense purple color.

EXAMPLE 3

A. A solution of 67.2 g (0.4 mole) of 4-nitrophthalic anhydride and 63.0g (0.32 mole) of 80.6 percent active 1-ethyl-2-methylindole in 50 ml ofethylene dichloride was heated at reflux for two hours. The reactionmixture was then allowed to cool to room temperature. The yellowprecipitate which separated was collected by filtration, washed withfresh ethylene dichloride and dried to obtain 64.5 g of2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]-5-nitrobenzoic acid (FormulaVIII: R°═R² ═R³ ═Y¹ ═H; R¹ ═NO₂ ; R⁵ ═CH₃ ; R⁶ ═CH₂ CH₃) having ameltingpoint of 203°-204° C.

B. A mixture of 3.68 g (0.01 mole) of2-[(1-ethyl-2-methyl3-indolyl)carbonyl]-5-nitrobenzoic acid, prepared asdescribed in part A above, and 2.0 g (0.012 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine in 10.0 ml of acetic anhydridewas heated at 90° C. for one hour and then allowed to cool to 25° C. Thesolid which separated was collected by filtration, washed withdiethylether and dried to obtain 3.8 g of3-[2,4-bis(dimethylamino)phenyl]-3(1-ethyl-2-methyl-3-indolyl)-6-nitrophthalide(Formula III: R°═R¹ ═R³ ═Y¹ ═H; R² ═NO₂ ; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂ ; R⁶═CH₂ CH₃) as an orange solid which melted over the range 185°-187° C.The nuclear magnetic resonance spectrum was in accord with the assignedstructure. A benzene solution of this product developed a black-purplecolor when spotted on silica gel.

C. A solution of 25.0 g (0.054 mole) of3-[2,4-bis(dimethylaamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-6-nitrophthalide,prepared as described in part B above, in 285 ml of concentratedhydrochloric acid was heated to 60° C. at which temperature 31.25 g(0.412 mole) of stannous chloride dihydrate was added at such a rate asto maintain the temperature at 60° C. After the addition was complete,the solution was heated to 70° C. and held there for a period of onehour and then allowed to cool to 25° C. The green-colored solid whichseparated was collected by filtration and was slurried in five percentaqueous sodium hydroxide solution. The resulting suspension wasextracted with 500 ml of toluene at room temperature and the tolueneextract was filtered, decolorized, and dried over sodium sulfate. Onstanding, a cream solid separated from the toluene solution. The solidwas filtered off and dried to obtain 2.9 g of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl2-methyl-3-indolyl)-6-aminophthalide(Formula III: R°═R¹ ═R³ ═Y¹ ═H; R² ═NH₂ ; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂ ; R⁶═CH₂ CH₃) having a melting point of 206°-209° C. Infrared analysisshowed a maximum at 1727 cm⁻¹ (C═O; s). The nuclear magnetic resonancespectrum was concordant with the assigned structure. A toluene solutionof the above compound developed an intense grape-black color whenspotted on a paper coated with phenolic resin.

D. To a solution of 7.04 g (0.02 mole) of2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]-5-nitrobenzoic acid, preparedas described in part A of this example, in 70 ml of concentratedhydrochloric acid, there was added 13.5 g (0.06 mole) of stannouschloride dihydrate at such a rate as to allow the reaction to exothermto 55° C. The temprature was maintained at 55° C. for an additionalone-half hour. The reaction was then cooled to room temprature and thepH adjusted to six by the addition of 10 percent aqueous sodiumhydroxide solution. The red precipitate thus formed was filtered off andextracted into acetone. The acetone solution was evaporated and thepaste-like residue was slurried in diethylether and then the solid wascollected by filtration to obtain 3.5 g of2-[(1-ethyl-2-methyl-3-indolyl)-carbonyl]-5-aminobenzoic acid (FormulaVIII: R³ ═R² ═R°═Y¹ ═H; R¹ ═NH₂ ; R⁵ ═CH₃ ; R⁶ ═CH₂ CH₃), a red solidwhich melted at 187°-189° C.

E. A mixture of 3.22 g (0.01 mole) of2-[(1-ethyl-2-methyl3-indolyl)carbonyl]-5-aminobenzoic acid, 118 g (0.01mole) of N,N,N',N'-tetramethyl-m-phenylenediamine in 10.0 ml of aceticanhydride was heated to 50° C. for one-half hour. After cooling toambient temperature, 50 ml of water was added and the reaction mixturewas filtered. The filtrate was rendered alkaline with dilute aqueoussodium hydroxide in the presence of 100 ml of toluene. The toluene layerwas separated, dried and evaporated to obtain as tan crystals3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-6-acetamidophthalide(Formula III: R°═R¹ ═R³ ═Y¹ ═H; R² ═NHCOCH₃ ; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂ ;R⁶ ═CH₂ CH₃) having a melting point of 204°-206° C. Infrared analysesshowed maxima at 1733 cm⁻¹ (C═O; s) and 1695 cm⁻¹ (C═O; s). Nuclearmagnetic resonance analsis was consistent with the structure. An acetonesolution of the above compound developed an intense grape color whenspotted on silica gel.

EXAMPLE 4

A. Following the procedure described in part A of Example 1, 7.4 g (0.05mole) of phthalic anhydride, 16.0 g (0.07 mole) of 79 percent active1-n-butyl-2-methylindole and 13.3 g (0.01 mole) of aluminum chloridewere interacted in 50 ml of benzene to obtain2-[(1-n-butyl-2-methyl-3-indolyl)carbonyl]benzoic acid (Formula VIII:R°═R¹ ═R² ═R³ ═Y¹ ═H; R⁵ ═CH₃ ; R⁶ ═(CH₂)₃ CH₃) a pale pink solidmelting over the range 88°-92° C. The nuclear magnetic resonancespectrum was consistent with the structure. Infrared maxima wererecorded at 1720 cm⁻¹ (C═O; s) and 1700 cm⁻¹ (C═O; s).

B. A mixture of 3.35 g (0.01 mole) of2[(1-n-butyl-2-methyl-3-indolyl)carbonyl]benzoic acid, prepared asdescribed in part A above, 1.80 g (0.011 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine and five ml of acetic anhydridewas stirred at ambient temperature for a period of approximately 18hours The reaction mixture was then poured into a mixture of 40 ml ofwater, 40 ml of ligroin and 20 ml of 10 percent aqueous sodiumhydroxide. The ligroin layer was separated and the white crystals whichseparated from the solution on standing, were collected by filtrationand dried to obtain3-[2,4-bis(dimethylamino)phenyl]-3-(1-n-butyl-2-methyl-3-indolyl)phthalide(Formula III: R°═R¹ ═R² ═R³ ═Y¹ ═H; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂ ; R⁶ ═(CH₂)₃CH₃) which melted at 165°-167° C. A characteristic infrared maximumappeared at 1752 cm⁻¹ (C═O; s). A toluene solution of the productspotted on silica gel developed an intense purple-colored image.

C. In a manner similar to that described in part B above, 3.35 g (0.01mole) of 2[(1-n-butyl-2-methyl-3-indolyl)carbonyl]-benzoic acid and 2.42g (0.011 mole) of N,N,N',N'-tetraethyl-m-phenylenediamine wereinteracted to obtain3-[2,4-bis(diethylamino)phenyl]-3-(1-n-butyl-2-methyl-3-indolyl)phthalide(Formula III: R°═R¹ ═R² ═R³ ═Y¹ ═H; R═CH₂ CH₃ ; R⁴ ═N(CH₂ CH₃)₂ ; R⁵═CH₃ ; R⁶ ═(CH₂)₃ CH₃), as tan-colored crystals which melted at 78°-80°C. A toluene solution of the product spotted on silica gel developed anintense blue-black-colored image.

EXAMPLE 5

A. In a manner similar to that described in part A of Example 1hereinabove, 7.4 g (0.05 mole) of phthalic anhydride, 16.0 g (0.053mole) of 76.5 percent active 1-n-octyl-2-methylindole, and 13.3 g (0.1mole) of aluminum chloride were interacted in 50 ml of benzene to obtain6.9 g of 2-[(1-n-octyl-2-methyl-3-indolyl)carbonyl]benzoic acid (FormulaVIII: R°═R¹ ═R² ═R³ ═Y¹ ═H; R⁵ ═CH₃ ; R⁶ ═(CH₂)₇ CH₃), as a pink-coloredpowder which melted at 121°-123° C. The nuclear magnetic spectrum was inagreement with the structure and a significant maxima occurred at 1717cm⁻¹ (C═O; s).

B. Proceeding in a manner similar to that described in part B of Example4 above, 3.91 g (0.01 mole) of2-[(1-n-octyl2-methyl-3-indolyl)carbonyl]benzoic acid, 1.80 g (0.011mole) of N,N,N'N'-tetramethyl-m-phenylenediamine and five ml of aceticanhydride were interacted at ambient temprature for a period ofapproximately 24 hours to obtain, after recrystallization from methanol,3-[2,4-bis(dimethylamino)phenyl]-3-(1-n-octyl-2-methyl-3-indolyl)phthalide(Formula III: R°═R¹ ═R² ═R³ ═Y¹ ═H; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂ ; R⁶ ═(CH₂)₇CH₃) which melted over the range 64°-68° C. A significant infraredabsorption was observed at 1750 cm⁻¹ (C═O; s). Analysis by mass spectrumshowed m/e peaks at 537 (M³⁰ ) and 493 (M⁺ --CO₂). A toluene solution ofthe product when spotted on a phenolic resin coated paper developed anintense grape-colored image.

EXAMPLE 6

A. Proceeding in a manner similar to that described in part A of Example2, 14.3 g (0.05 mole) of tetrachlorophthalic anhydride, 16.0 g (0.07mole) of 76 percent active 1-n-butyl-2-methyindole and 13.3 g (0.10mole) of aluminum chloride were interacted in 100 ml of benzene. Thereaction mixture was drowned in 200 ml of five percent hydrochloric acidwith stirring. The solid which formed was collected by filtration,washed with water and dried to obtain2-[(1-n-butyl-2-methyl3-indolyl)carbonyl]-3,4,5,6-tetrachlorobenzoicacid (Formula VIII: R°═R¹ ═R² ═R³ ═Y¹ ═H; R⁵ ═CH₃ ; R⁶ ═(CH₂)₃ CH₃), apale yellow solid melting at 162°-164° C. The nuclear magnetic resonancespectrum was in accord with the structure.

B. A mixture of 5.20 g (0.01 mole) of2-[(1-n-butyl-2-methyl-3-indolyl)carbonyl]-3,4,5,6-tetrachlorobenzoicacid, prepared in part A above, 2.0 g (0.012 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine and five ml of acetic anhydridewas warmed over a period of approximately forty minutes at 100° C. Thereaction mixture was then cooled to ambient temperature, set asideovernight, rendered alkaline with 10 percent aqueous sodium hydroxidesolution and extracted with benzene. Petroleum ether was slowly added tothe separated benzene extract and the solid which slowly separated wascollected by filtration and dried to obtain3-[2,4-bis(dimethylamino)phenyl]-3-(1-n-butyl-2-methyl3-indolyl)-4,5,6,7-tetrachlorophthalide(Formula III: R°═R¹ ═R² ═R³ ═Cl; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂ ; R⁶ ═(CH₂)₃CH₃ ; Y¹ ═H), as white crystals having a melting point of 173°-175° C.The nuclear magnetic resonance spectrum was consistent with thestructure; a maximum of 1770 cm⁻¹ (C═O; s) appeared in the infraredspectrum; the spectrum showed a m/e peak at 617 (M⁺, 4 Cl).

EXAMPLE 7

A. Proceeding in the same manner as that described in part A of Example6 above, 14.3 g (0.05 mole) of tetrachlorophthalic anhydride, 16.0 g(0.052 mole) of 76.5 percent active 1-n-octyl-2-methylindole and 13.3 g(0.10 mole) of aluminum chloride were interacted to obtain2-[(1-n-octyl-2-methyl-3-indolyl)carbonyl[-3,4,5,6-tetrachlorobenzoicacid (Formula VIII: R°═R¹ ═R² ═R³ ═Cl; R⁵ ═CH₃ ; R⁶ ═(CH₂)₇ CH₃ ; Y¹═H), a pale orange solid melting at 132°-134° C. The infrared spectrum,showing a maximum at 1745 cm⁻¹ (C═O; s) and the nuclear magneticresonance spectrum was in accord with the structure.

B. A mixture of 2.64 g (0.005 mole) of2-[1-n-octyl-2-methyl-3-indolyl)carbonyl]-3,4,5,6-tetrachlorobenzoicacid, prepared as described in part A above, 1.0 g (0.006 mole) ofN,N,N'N'-tetramethyl-m-phenylenediamine and three ml of acetic anhydridewere interacted as described in Example 2, part C above to obtain3-[2,4-bis(dimethylamino)phenyl]-3-(1-n-octyl-2-methyl3-indolyl)-4,5,6,7-tetrachlorphthalide(Formula III: R°═R¹ ═R² ═R³ ═Cl; R═CH₃ ; R⁴ ═N(CH₃)₂ ; R⁵ ═CH₃ ; R⁶═(CH₂)₇ CH₃ ; Y¹ ═H), a pale yellow powder melting at 145°-147° C. Theinfrared spectrum showed a maximum appearing at 1770 cm⁻¹ (C═O; s) andthe nuclear magnetic resonance spectrum was concordant with thestructure.

EXAMPLE 8

A. A suspension of 14.8 g (0.10 mole) of phthalic anhydride, 10.5 g(0.05 mole) of 2-phenylindole and 82 ml of xylene was heated to 110° C.briefly, cooled to and maintained at 95° C. for approximately two hours.The solution was cooled to ambient temperature and the solid whichseparated was collected by filtration and dried to obtain 10.6 g of2-[(2-phenyl-3-indolyl)-carbonyl]benzoic acid (Formula VIII: R°═R¹ ═R²═R³ ═R⁶ ═Y¹ ═H; R⁵ ═C₆ H₅) which melted at 106°-107° C. and had anuclear magnetic resonance spectrum consistent with the assignedstructure.

B. A mixture of 4.82 g (0.014 mole) of the2-[(2-phenyl3-indolyl)carbonyl]benzoic acid from part A above, 3.60 g(0.02 mole) of N,N,N',N'-tetramethyl-m-phenylenediamine, and five ml ofacetic anhydride was slowly heated until a purple color formed andmaintained at this temperature for approximately two hours. Aftercooling to room temperature, sufficient 3N hydrochloric acid was addedto the mixture to effect solution and stirring was continued forapproximately 1.5 hours The resulting solution was filtered and the pHadjusted to five by the addition of sodium acetate. The precipitatewhich separated from the solution was collected by filtration and driedto obtain3-[2,4-bis(dimethylamino)phenyl[-3-(2-phenyl-3-indolyl)phthalide(Formula III: R°═R¹ ═R² ═R³ ═R⁶ ═Y¹ ═H; R═CH₃ ; R⁴ ═N(CH₃)₂ ; R⁵ ═C₆ H₅9. After recrystalization from toluene and hexane, the off white-coloredsolid melted at 153°-155° C. Significant infrared maxima were observedat 3380 cm⁻¹ (NH; m) and 1750 cm⁻¹ (C═O; s). The nuclear magneticresonance spectrum was consistent with the structure. A toluene solutionof this product spotted on silica gel developed an intensegrape-red-colored image.

EXAMPLE 9

A. Proceeding in a manner similar to part A of Example 8, butsubstituting 2-methylindole for 2-phenylindole, there was obtained2-[(2-methyl-3-indolyl)carbonyl]benzoic acid (Formula VIII: R°═R¹ ═R²═R³ ═R₆ ═Y¹ ═H; R⁵ ═CH₃), as pale pink-colored crystals melting at198°-200° C.

B. A mixturwe of 8.37 g (0.03 mole) of2-[(2-methyl-3-indolyl)carbonyl]benzoic acid, prepared as described inpart A above, 8.37 g (0.05 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine and 10 ml of acetic anhydridewas interacted at 50° C. as described in part B of Example 8 above toobtain 3-[2,4-bis(dimethylamino)phenyl]-3-(2-methyl-3-indolyl)phthalide(Formula III: R°═R¹ ═R² ═R³ ═R⁶ ═Y¹ ═H; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂). Afterpurification by slurrying in a benzene and ligroin mixture, thecollected and dried product melted at 183°-186° C. The product had massspectrum with a m/e peak at 425 (M⁺). Both the infrared and nuclearmagnetic resonance spectra were consistent with this structure. Atoluene solution of the product spotted on a phenolic resin coated paperdeveloped an intense grape-colored image.

EXAMPLE 10

A. A mixture of 5.0 g (0.03 mole) of 5-methoxy-2-methylindole and 4.6 g(0.03 mole) of phthalic anhydride in 25 ml of ethylene dichloride wasrefluxed for ten hours, cooled to room temperature and the separatedsolid was collected by filtration and dried to obtain2-[(2-methyl-5-methoxy-3-indolyl)carbonyl]benzoic acid (Formula VIII:R°═R¹ ═R² ═R³ ═R⁶ ═H; R⁵ ═CH₃ ; Y¹ ═OCH₃), as a pale pink-colored solidwhich decomposed at 203°-204° C. The nuclear magnetic resonance andinfrared spectra were consistent with the assigned structure.

B. A mixture of 2.0 g (0.006 mole) of2-[(2-methyl-5-methoxy-3-indolyl)carbonyl]benzoic acid, obtained asdescribed in part A above, 1.1 g (0.0067 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine and six ml of acetic anhydridewere interacted at 50°-55° C. in a manner similar to that described inExample 2, part B to obtain 2.5 g of3-[2,4-bis(dimethylamino)-phenyl]-3-(2-methyl-5-methoxy-3-indolyl)phthalide(Formula III: R°═R¹ ═R² ═R³ ═R⁶ ═H; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂ ; Y¹ ═OCH₃),as a light pink-colored solid melting at 196°-198° C. withdecomposition. The infrared spectrum, showing a significant maximum at1740 cm⁻¹ (C═O; s) and the nuclear magnetic resonance spectrum were inaccord with the structure. A toluene solution of this product spotted ona phenolic resin coated paper developed an intense violet-colored image.

EXAMPLE 11

A. A mixture of 5.0 g (0.034 mole) of phthalic anhydride and 5.0 g(0.034 mole of 2,5-dimethylindole in 30 ml of ethylene dichloride wasrefluxed for 20 hours, cooled and the separated solid filtered off anddried to obtain 3.8 g of 2-[(2,5-dimethyl-3-indolyl)carbonyl]benzoicacid (Formula VIII: R°═R¹ ═R² ═R³ ═R⁶ ═H; R⁵ ═CH₃ ; Y¹ ═CH₃), as apink-colored solid melting at 198°-200° C.

B. A mixture of 2.0 g (0.007 mole) of2-[(2,5-dimethyl-3-indolyl)carbonyl]benzoic acid from part A above, 1.1g (0.007 mole) of N,N,N',N'-tetramethyl-m-phenylenediamine and seven mlof acetic anhydried was interacted in a manner similar to that describedin Example 3, part E above, to obtain 2.35 g of3-[(2,4-bis(dimethylamino)phenyl]-3(2,5-dimethyl-3-indolyl)phthalide(Formula III: R°═R¹ ═R² ═R³ ═R⁶ ═H; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂ ; Y¹ ═CH₃),a light purple solid melting over the range of 100°-125° C. The infraredshowed a characteristic absorpotion maximum at 1760 cm⁻¹ (C═O; s). Atoluene solution of this product spotted on acid clay or phenolic resindeveloped an intense violet-colored image.

EXAMPLE 12

A mixture of 1.55 g (0.0036 mole) of2-[(1,2-dimethyl-3-indolyl)carbonyl]-3,4,5,6-tetrabenzoic acid preparedin a manner similar to part A of Example 2, 0.58 g (0.0035 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine and ten ml of acetic anhydridewas heated to reflux for approximately one hour. After cooling to roomtemperature, the reaction mixture was poured into 20 ml of 10 percenthydrochloric acid and the mixture then rendered alkaline by the additionof concentrated ammonium hydroxide. The purple solid which separated wascollected by filtration, dried, and crystallized twice from isopropylacetate to obtain3-[(2,4-bis(dimethylamino)phenyl]-3-(1,2-dimethyl-3-indolyl)-4,5,6,7-tetrachlorophthalide(Formula III: R°═R¹ ═R² ═R³ ═Cl; R═R⁵ ═R⁶ ═CH₃ ; R⁴ ═N(CH₃)₂ ; Y¹ ═H)which decomposed at 228°-229° C. The mass spectrum showed an m/e at 575(M⁺, 4 Cl). A toluene solution of the product spotted on silica geldeveloped an intense purple-colored image.

EXAMPLE 13

A suspension of 1.36 g (0.01 mole) of m-amino-N,N-dimethylaniline in 20of acetic anhydride was heated to 80°-90° C. for approximately thirtyminutes and then cooled to room temperature. Three grams (0.01 mole) of2-[(1-ethyl-2-methyl-3-indolyl)-carbonyl]benzoic acid, prepared asdescribed in part A of Example 1, was added and the resulting mixturewas heated at 60°-70° C. for approximately thirty minutes. Aftercooling, the reaction mixture was poured into 100 ml of 10 percenthydrochloric acid and the mixture made alkaline with 10 percent aqueoussodium hydroxide with the addition of ice. The solid which separated wascollected by filtration and dried to obtain3-[(2-acetamido-4-dimethylamino-phenyl]-3-(1-ethyl-2-methyl-3-indolyl)phthalide(Formula III: R°═R¹ ═R² ═R³ ═Y¹ ═H; ##STR27## R═R⁵ ═CH₃ ; R⁶ ═CH₂ CH₃)as a pale blue-colored solid melting over the range 180°-195° C.Infrared absorption maxima appeared at 1757 cm⁻¹ (C═O; s) and 1696 cm⁻¹(C═O; s).

EXAMPLE 14

A mixture of 0.34 g (0.001 mole) of2-[(1,2-dimethyl-3-indolyl)carbonyl]-5-dimethylaminobenzoic acidprepared as described in Example 1 of U.S. Pat. No. 3,540,910 wasinteracted with 0.16 g (0.001 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine in 5 ml of acetic anhydried ina similar manner to the procedure described in Example 1, part Chereinabove to obtain3-[2,4-bis(dimethylamino)phenyl]-3-(1,2-dimethyl-3-indolyl)-6-dimethylaminophthalide(Formula III: R°═R¹ ═R³ ═Y¹ ═H; R² ═N(CH₃)₂ ; R═R⁵ ═R⁶ ═CH₃ ; R⁴═N(CH₃)₂) which melts over the range of 146°-152° C. A significantinfrared absorption maximum appeared at 1760 cm⁻¹ (C═O; s). A toluenesolution of this product spotted on silica gel developed an intensegrape-red-colored image.

EXAMPLE 15

A. To a mixture of 8.17 g (0.05 mole) of N-ethylcarbazole and 3.7 g(0.025 mole) of phthalic anhydride in 112 g of chlorobenzene, 6.65 g(0.05 mole) of aluminum chloride was added in small increments atambient temperature after which the mixture was warmed in the range of50°-70° C. for two hours. The reaction mixture was poured onto ice andrendered acidic by the addition of 10 percent hydrochloric acid. Thechlorobenzene layer was separated and steam:distilled to remove thechlorobenzene. The residue was extracted with 10 percent agueous sodiumhydroxide, filtered to remove the insolubles and then acidified withdilute hydrochloric acid. The solid which separated was collected byfiltration, washed with water and dried to obtain2-[(9-ethyl-3-carbazolyl)carbonyl]benzoic acid (Formula VII: R°═R¹ ═R²═R³ ═H; R⁸ ═CH₂ CH₃) melting over the range 120°-130° C.

B. A mixture of 3.43 g (0.01 mole) of2-[(9-ethyl-3-carbazolyl)carbonyl]benzoic acid, 1.80 g (0.011 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine and 4.0 ml of acetic anhydridewas interacted in a manner similar to that described in Example 1, partC above to yield3-[2,4-bis(dimethylamino)phenyl]-3-(9-ethyl-3-carbazolyl)pythalide(Formula V: R°═R¹ ═R² ═R³ ═H; R═CH₃ ; R⁴ ═N(CH₃)₂ ; R⁸ ═CH₂ CH₃) whichmelted over the range 134°-142° C. A significant infrared absorptionmaximum appeared at 1753 cm⁻¹ (C═O; s). A toluene solution of thisproduct spotted on silica gel developed a bordeaux-colored image.

EXAMPLE 16

A. To a mixture of 2.96 g (0.02 mole) of phthalic anhydride and 5.72 g(0.04 mole) of N-phenylpyrrole in 50 ml of chlorobenzene, maintained at0°-5° C. in an ice bath, 810 g (0.06 mole) of aluminum chloride wasadded in small portions. The reaction mixture was held at 0°-5° C. forapproximately two hours. The reaction was allowed to warm to roomtemperature and then set aside overnight at ambient temperature. Thereaction mixture was worked up in a manner similar to that described inpart A of Example 15 to obtain 2-[(1-phenyl-2-pyrrolyl)carbonyl]benzoicacid (Formula IX: R°═R¹ ═R² ═R³ ═H; R⁷ ═C₆ H₅) which melted over therange 159°-168° C.

B. A mixture of 2.91 g (0.01 mole) of2-[(1-phenyl-2-pyrrolyl)carbonyl]benzoic acid prepared in part A above,2.34 g (0.017 mole) of 84.6 percent activeN,N,N',N'-tetramethyl-m-phenylenediamine in 4.0 ml of acetic anhydridewas interacted in a manner similar to that described in Example 1, partC to obtain 2.61 g of3-[2,4-bis(dimethylamino)phenyl]-3-(1-phenyl-2-pyrrolyl)phthalide(Formula IV: R°═R¹ ═R² ═R³ ═H; R═CH₃ ; R⁴ ═N(CH₃)₂ ; R⁷ ═C₆ H₅), apeach-colored powder melting at 193°-194° C. The infrared spectrumshowed a maximum at 1760 cm⁻¹ (C═O; s). A toluene solution of thisproduct spotted on silica gel developed an immediate orange-red-coloredimage.

EXAMPLE 17

A. Proceeding in a manner similar to that described in part A of Example16, 14.8 g (0.1 mole) of phthalic anhydride, 16.2 g (0.2 mole) ofN-methylpyrrole and 39.0 g (0.3 mole) of aluminum chloride wereinteracted in 50 ml of chlorobenzene to obtain2-[(1-methyl-2-pyrrolyl)carbonyl]benzoic acid (Formula IX: R°═R¹ ═R² ═R³═H; R⁷ ═CH₃) melting at 165°-167° C. A significant infrared absorptionmaximum appeared at 1710 cm⁻¹ (C═O; s).

B. A mixture of 4.58 g (0.02 mole) of2-[(1-methyl-2-pyrrolyl)carbonyl]benzoic acid, from part A above, 3.61 g(0.022 mole) of N,N,N',N'-tetramethyl-m-phenylenediamine and 3.0 ml ofacetic anhydride was interacted in a manner similar to that describedabove in Example 1, part C to obtain 1.92 g of3-[2,4-bis(dimethylamino)phenyl]-3-(1-methyl-2-pyrrolyl)phthalide(Formula IV: R°═R¹ ═R² ═R³ ═H; R═R⁷ ═CH₃ ; R⁴ ═N(CH₃)₂), a tan powdermelting at 148°-150° C. A toluene solution of this product spotted onsilica gel developed an intense red-colored image.

EXAMPLE 18

A. A stirred solution of 48.0 g (0.250 mole) of trimellitic anhydrideand 45.0 g (0.314 mole) of 1-ethyl-2-methylindole in 350 ml of ethylenedichloride was heated at reflux for a period of approximately two hours,and then allowed to cool to ambient temperature. The solid, whichseparated, was collected by filtration, washed with 200 ml of ethylenedichloride and dried in vacuo at 60° C. to obtain 66.0 g of4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid(Formula VIII: R¹ ═R² ═H/COOH; R°═R³ ═Y¹ ═H; R⁵ ═CH₃ ; R⁶ ═CH₂ CH₃), ayellowish-orange solid melting over the range 198°-201° C. Infraredmaxima appeared at 1730 (C═O; s) and 1700 cm⁻¹ (C═O; vs). The nuclearmagnetic resonance spectrum was in agreement with the assignedstructure.

B. A stirred mixture of 17.5 g (0.05 mole) of the4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid,prepared as described in part A above, 8.5 g (0.052 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine and 25 ml of acetic anhydridewas heated at 50° C. for a period of two hours and then allowed to coolto ambient temperature. After the addition of 25 ml of isopropylalcohol, the resulting mixture was poured into water with vigorousstirring. The solid which separated was collected by filtration, washedwith water and dried in vacuo at 60° C. to obtain 22.0 g of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-3-methyl-3-indolyl)-5/6-carboxyphthalide(Formula III: R═R⁵ ═CH₃ ; R°═R³ ═Y¹ ═H; R¹ ═R² ═H/COOH; R⁴ ═N(CH₃)₂ ; R⁶═CH₂ CH₃) as a dark purple solid melting over the range 149°-151° C.Infrared maxima appeared at 1775 (C═O; s) and 1720 cm⁻¹ (C═O; s).

C. Three milliliters of dimethyl sulfate was added to a refluxingmixture of 3.0 g of the3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in part B above, 3.0 g of potassium carbonate and100 ml of acetone. The reaction mixture was heated at reflux for aperiod of two hours and was then poured into water and the agueousmixture extracted with toluene. The toluene extract was washedsuccessively with water and saturated salt solution and then evaporatedto dryness. The residue was triturated with ligroin (b.p. 60°-90° C.)and the solid separated and dried to obtain 1.0 g of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide(Formula III: R═R⁵ ═CH₃ ; R°═R³ ═Y¹ ═H; R¹ ═R² ═H/COOCH₃ ; R⁴ ═N(CH₃)₂ ;R⁶ αCH₂ CH₃), a light purple solid melting over the range 72°-85° C.Infrared maxima appeared at 1760 (C═O; s) and 1730 cm⁻¹ (C═O; s).Analysis by mass spectrum showed m/e peaks at 511 (M⁺) and at 452 (M⁺--CO₂ CH₃). A toluene solution of the produce spotted on silica gel, anacidic clay or a phenolic resin developed a grape-colored image.

EXAMPLE 19

To a stirred solution of 6.38 g (0.013 mole) of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide,prepared as described above in part B of Example 18, 150 ml ofhexamethylphosphoramide and 10 ml of 25 percent aqueous sodiumhydroxide, there was added 7.0 ml of ethyl iodide. The mixture wasstirred at room temperature for a period of two hours. The reactionmixture was then drowned in water and the aqueous mixture was extractedwith toluene. The toluene layer was washed with water, dried overanhydrous sodium sulfate, and evaporated. The residue was trituratedwith ligroin (b.p. 60°-90° C.) and the separated solid collected anddried to obtain 0.92 g of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-ethoxycarbonylphthalide(Formula III: R═R⁵ ═CH₃ ; R°═R³ ═Y¹ ═H; R¹ ═R² ═H/COOCH₂ CH₃ ; R⁴═N(CH₃)₂ ; R⁶ ═CH.sub. 2 CH₃), a light brown powder melting over therange 88°-97° C. Infrared maxima appeared at 1765 (C═O; s) and 1725 cm⁻¹(C═O; s). The nuclear magnetic resonance spectrum was in agreement withthe assigned structure. Analysis by mass spectrum showed m/e peak at 525(M⁺). A toluene solution of the product spotted on silica gel, an acidicclay or a phenolic resin developed a grape-colored image.

EXAMPLE 20

Following a procedure similar to that described above in part C ofExample 18 but substituting dimethylformamide for acetone and n-octylbromide for dimethyl sulfate, there was obtained3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-n-octyloxycarbonylphthalide(Formula III: R═R⁵ ═CH₃ ; R°═R³ ═Y¹ ═H; R¹ ═R² ═H/COO(CH₂)₇ CH₃ ; R⁴═N(CH₃)₂ ; R⁶ ═CH₂ CH₃) as a light brown oil. Infrared maxima appearedat 1770 (C═O; s) and 1730 cm⁻¹ (C═O; s). A benzene solution of theproduct spotted on silica gel, an acidic clay or a phenolic resindeveloped a grape-colored image.

EXAMPLE 21

Following a procedure similar to that described above in Example 20except that α-bromotoluene was used in place of n-octyl bromide, therewas obtained 2.52 g of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-phenylmethoxycarbonylphthalide (Formula III: R═R⁵ ═CH₃ ; R°═R³ ═Y¹ ═H; R¹ ═R²═H/COOCH₂ C₆ H₅ ; R⁴ ═N(CH₃)₂ ; R⁶ ═CH₂ CH₃) a light purple powdermelting over the range 72°-78° C. Infrared maxima appeared at 1770 cm⁻¹(C═O; s). Analysis by mass spectrum showed m/e peaks at 587 (M⁺) and 543(M⁺ --CO₂). A tolune solution of the product spotted on silica gel, anacidic clay or a phenolic resin developed a grape-colored image.

EXAMPLE 22

A. A mixture of 35 g (0.10 mole) of4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acidprepared as described in Example 18, part A above, 20 g (0.103 mole) ofN,N-diethyl-m-phenetidine and 60 ml of acetic anhydride was stirred atroom temperature for a period of approximately eighteen hours. After theaddition of 100 ml of isopropyl alcohol, the resulting mixture waspoured into water with vigorous stirring. The solid which separated wascollected by filtration, washed with water and dried to obtain 53.4 g of3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R°═R³ ═Y¹ ═H; R¹ ═R² ═H/COOH; R⁴ ═OC₂ H₅ ;R⁵ ═CH₃), a dark blue solid melting over the range of 130°-144° C.Infrared maxima appeared at 1765 (C═O; s) and 1725 cm⁻¹ (C═O; s).Analysis by mass spectrum showed m/e peaks at 526 (M⁺) and 481 (M⁺ --CO₂H).

B. Employing a procedure similar to that described in part C of example18, but interacting 5.0 g (0.0095 mole) of3(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-3-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in part A of this example with dimethyl sulfateinstead of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide,there was obtained 4.9 g of3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R°═R³ ═Y¹ ═H; R¹ ═R² ═H/COOCH₃ ; R⁴ ═OC₂ H₅; R⁵ ═CH₃), a light green-colored solid melting over the range 96°-103°C. Infrared maxima appeared at 1765 (C═O; s) and 1730 cm⁻¹ (C═O; s). Thenuclear magnetic resonance spectrum was in agreement with the assignedstructure. Analysis by mass spectrum showed m/e peaks at 540 (M⁺), 496(M⁺ --CO₂) and 418 (M⁺ --COOCH₃). A toluene solution of the producespotted on silica gel, an acidic clay or a phenolic resin developed adeep blue-colored image which had good lightfastness.

EXAMPLE 23

When diethyl sulfate was substituted for dimethyl sulfate forinteraction with3(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideaccording to the procedure described in part B of Example 22, there wasobtained 1.5 g of3(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-ethoxycarbonylphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R°═R³ ═Y¹ ═H; R¹ ═R² ═H/COOCH₂ CH₃ ; R⁴ ═OC₂H₅ ; R⁵ ═(CH₃ ;), a light yellow solid melting over the range 141°-148°C. Infrared maxima appeared at 1750 (C═O; s) and 1732 cm⁻¹ (C═O; s).Analysis by mass spectrum showed m/e peaks at 554 (M⁺), 510 (M⁺ --CO)and 481 (M⁺ --CO₂ C₂ H₅). A toluene solution of the product spotted onsilica gel, an acidic clay or a phenolic resin developed a deepblue-colored image which had good lightfastness.

EXAMPLE 24

Following a procedure similar to that described above in Example 22,part B, 5.0 g (0.0095 mole) of3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in Example 22, part A was interacted with 2.0 g(0.0117 mole) of α-bromotoluene to obtain 3.4 g of3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-idolyl)-5/6-phenylmethoxycarbonylphthalide(Formula III: R═,R⁶ ═C₂ H₅ ; R°═R³ ═Y¹ ═H; R¹ ═R² ═H/COOCH₂ C₆ H₅ ; R⁴═OC₂ H₅ ; R⁵ ═CH₃), a light yellow solid melting over the range 82-87°C. Infrared maxima appeared at 1765 (C═O; s) and 1725 cm⁻¹ (C═O; s).Analysis by mass spectrum showed m/e peaks at 616 (M⁺) and 572 (M⁺--CO₂). A toluene solution of the product spotted on silica gel, anacidic clay or a phenolic resin developed a deep blue-colored imagewhich had good lightfastness.

EXAMPLE 25

When n-octyl bromide was substituted for α-bromotoluene for interactionwith3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideaccording to the procedure described in Example 24, there was obtained3-(2-ethyoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-n-octoxycarbonylphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R°═R³ ═Y¹ ═H; R¹ ═R² ═H/COO-n-(CH₂)₇ CH₃ ;R⁴ ═OC₂ H₅ ; R⁵ ═CH³), a light blue solid melting over the range134°-162° C. A toluene solution of the product spotted on silica gel, anacidic clay or a phenolic resin developed a deep blue-colored imagewhich had good lightfastness.

EXAMPLE 26

Substituting 1-bromohexadecane for n-octyl bromide for interaction with3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideaccording to the procedure described in Example 25, there was obtained7.1 g of3-(2-ethoxy-4-diethylaminnophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-hexadecanoxycarbonylphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R°═R³ ═Y¹ ═H/COO(CH₂)₁₅ CH₃ ; R⁴ ═OC₂ H₅ ;R⁵ ═CH₃), a light brown oil. Infrared maxima appeared at 1765 (C═O; s)and 1725 cm⁻¹ (C═O; s). Thenuclear magnetic resonance spectrum was inagreement with the assigned structure. Analysis by mass spectrum showedm/e peaks at 750 (M⁺) and 706 (M⁺ --CO₂). A benzene solution of theproduct spotted on silica gel, an acidic clay or phenolic resindeveloped a deep blue-colored image which had good lightfastness.

EXAMPLE 27

To a stirred solution of 5.3 g of3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in Example 22, part A, in 25 ml of acetone therewas added 2.6 of 1,1,3,3-tetramethylbutylamine. The mixture was stirredat ambient temperature for approximately ten minutes and then 160 ml ofn-hexane was added. The supernatant liquid was decanted and theinsoluble, brown, gummy residue triturated with n-hexane to obtain 6.2 gof the 1,1,3,3-tetramethylbutylammonium salt of3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula III: R°═R³ ═Y¹ ═H; R¹ ═R² ═H/CO.sup.⊖ ON.sup.⊕ H₃ C(CH₃)₂ CH₂C(CH₃)₂ CH₃ ; R═R⁶ ═C₂ H₅ ; R⁴ ═OC₂ H₅ ; R⁵ ═CH₃), a beige-colored solidmelting over the range of 80°-105° C. with decomposition. Infraredspectral analysis showed significant maxima in the range from 2350 cm⁻¹to 2150 cm⁻¹, and a strong absorption at 1760 cm⁻¹ (C═O; s). Theassigned structure was corroborated by a concordant nuclear magneticresonance spectrum. A toluene solution of the product spotted on silicagel, an acidic clay or a phenolic resin developed a deep blue-coloredimage which had good lightfastness. This product is also a water-solublecolor-former.

EXAMPLE 28

A. Following a procedure similar to that described in part A of Example22 but interacting, N,N-dimethylaniline instead ofN,N-diethyl-m-phenetidine, with4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, therewas obtained3-(4-dimethyl-aminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula III: R═R⁵ ═CH₃ ; R°═R³ ═R⁴ ═Y¹ ═H; R¹ ═R² ═H/COOCH; R⁶ ═C₂ H₅),a blue-colored solid melting over the range 141°-160° C. Infrared maximaappeared at 1770 (C═O; s) and 1730 cm⁻¹ (C═O; s). Analysis by massspectrum showed m/e peaks at 454 (M⁺), 410 (M⁺ --CO₂) and 409 (M⁺--COOH).

B. Employing a procedure similar to that described in part C of Example18, but substituting3-(4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in part A above for3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalidefor interaction with dimethyl sulfate, there was obtained3-(4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide(Formula III: R═R⁵ ═CH₃ ; R°═R³ ═R⁴ ═Y¹ ═H; R¹ ═R² ═H/COOCH₃ ; R⁶ ═C₂H₅), a light yellow solid melting over the range 101°-110° C. Infraredmaxima appeared at 1760 (C═O; s) and 1730 cm⁻¹ (C═O; s). The nuclearmagnetic resonance spectrum was in agreement with the assignedstructure. Analysis by mass spectrum showed m/e peaks at 468 (M⁺), 424(M⁺ --CO₂) and 409 (M⁺ --COOCH₃). A toluene solution of the productspotted on silica gel, an acidic clay or a phenolic resin developed ablue-colored image had good lightfastness.

EXAMPLE 29

Proceeding in a manner similar to that described above in Example 23,3-(4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in Example 28, part A, was interacted with diethylsulfate to obtain3-(4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-ethoxy-carbonylphthalide(Formula III: R═R⁵ ═CH₃ ; R°═R³ ═R⁴ ═Y¹ ═H; R¹ ═R² ═H/COOC₂ H₅ ; R⁶ ═C₂H₅), a light green solid melting over the range 114°-131° C. Infraredmaxima appeared at 1765 (C═O; s) and 1725 cm⁻¹ (C═O; s). Analysis bymass spectrum showed m/e peaks at 482 (M⁺), 438 (M⁺ --CO₂) and 409(M^(+--CO) ₂ C₂ H₅). A toluene solution of the product spotted on silicagel, an acidic clay or a phenolic resin developed a blue-colored imagewhich had good lightfastness.

EXAMPLE 30

When α-bromotoluene was substituted for diethyl sulfate in Example 29,there was obtained3-(4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-phenylmethoxycarbonylphthalide(Formula III: R═R⁵ ═CH₃ ; R°═R³ ═R⁴ ═Y¹ ═H; R¹ ═R² ═H/COOCH₂ C₆ H₅ ; R⁶═C₂ H₅), a light green-colored solid melting over the range 93°-98° C.Infrared maxima appeared at 1770 (C═O; s) and 1728 cm⁻¹ (C═O; s).Analysis by mass spectrum showed m/e peaks at 544 (M⁺) and 500(M^(+--CO) ₂). A toluene solution of the product spotted on silica gel,an acidic clay or a phenolic resin developed a blue-colored image whichhad good lightfastness.

EXAMPLE 31

A. Following a procedure similar to that described in part A of Example22, but using 15 g of N,N-diethylaniline instead ofN,N-diethyl-m-phenetidine for interaction with4/5-carboxy-2-](1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, therewas obtained3-(4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R°═R³ ═R⁴ ═Y¹ ═H; R¹ ═R² ═H/COOH; R⁵ ═CH₃),a blue solid melting over the range 169°-182° C. Infrared maximaappeared at 1765 (C═O; s) and 1730 cm⁻¹ (C═O; s). The nuclear magneticresonsance spectrum was in agreement with the assigned structure.

B. Proceeding in a manner similar to that described in part C of Example18, but using3-(4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in part A above in place of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalidefor interaction with dimethyl sulfate, there was obtained3-(4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6methoxycarbonylphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R°═R³ ═R⁴ ═Y¹ ═H; R¹═R² ═H/COOCH₃ ; R⁵═CH₃), a light green solid melting over the range 114°-128° C. Infraredmaxima appeared at 1765 (C═O; s) and 1730 cm³¹ 1 C═O; s). A toluenesolution of the product spotted on silica gel, an acidic clay or aphenolic resin developed a blue-colored image which had goodlightfastness.

EXAMPLE 32

A. Employing a procedure similar to that described in part A of Example22, but using m-chloro-N,N-dimethylaniline instead ofN,N-diethyl-m-phenetidine for interaction with4/5-carboxy-2-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid,there was obtained3-(2-chloro-4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula III: R═R⁵ CH₃ ; R°═R³ ═Y¹ ═H; R¹ ═R² ═H/COOH; R⁴ ═Cl; R⁶ ═C₂H₅), as a greenish-blue solid melting over the range 130°-142° C.Infrared maxima appeared at 1770 (C═O; s) and 1725 cm⁻¹ (C═O; m).

B. Proceeding in a manner similar to that described in part C of Example18, but using3-(2-chloro-4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6carboxyphthalideprepared as described in part A above instead of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalidefor interaction with dimethyl sulfate, there was obtained3-(2chloro-4-dimethyl-aminophenyl)-3-(1ethyl-2-methyl-3-indolyl)-5/6methoxycarbonyl-phthalide (Formula III: R═R⁵═CH₃ ; R°═R³ ═Y¹ ═H; R¹ ═R² ═H/COOCH₃ ; R⁴ ═Cl; R⁶ ═C₂ H₅), as a lightblue solid melting over the range 168°-193° C. Infrared maxima appearedat 1770 (C═O; s) and 1730 cm⁻¹ (C═O; s). A toluene solution of theproduct spotted on silica gel, an acidic clay or a phenolic resindeveloped a pale green-colored image.

EXAMPLE 33

A. Following a procedure similar to that described in part A of Example22, but using N,N-m-diethyltoluidine instead ofN,N-diethyl-m-phenetidine for interaction with4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, therewas obtained3-(2-methyl-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R°═R³ ═Y¹ ═H; R¹ ═R² ═H/COOH; R⁴ ═R⁵ ═CH₃),a turquoise-colored solid melting over the range 146°-162° C. Infraredmaxima appeared at 1765 (C═O; s) and 1720 cm⁻¹ (C═O; s). Analysis bymass spectrum showed m/e peaks at 496 (M⁺), 452 (M⁺ --CO₂) and 451 (M⁺--COOH).

B. Employing a procedure similar to that described in part C of Example18, but using2-(2-methyl-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in part A above instead of3-[2,4-bis(dimethylamino)-phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide,there was obtained3-(2-methyl-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3indolyl)-5/6-methoxycarbonylphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R°═R³ ═Y¹ ═H; R¹ ═R² ═H/COOCH₃ ; R⁴ ═R⁵═CH₃), a light yellow solid melting over the range 113°-120° C. Infraredmaxima appeared at 1770 (C═O; s) and 1730 cm⁻¹ (C═O; s). The nuclearmagnetic resonsance spectrum was in agreement with the assignedstructure. Analysis by mass spectrum showed m/e peaks at 510 (M⁺) and495 (M⁺ --COOCH₃). A toluene solution of the product spotted on silicagel, an acidic clay or a phenolic resin developed a turquiose-coloredimage which had good lightfastness.

EXAMPLE 34

Proceeding in a manner similar to that described above in Example 23,3-(2-methyl-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in Example 33, part A was interacted with diethylsulfate to obtain3-(2-methyl-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-ethoxycarbonylphthalide (Formula III: R═R⁶ ═C₂ H₅ ; R°═R³ ═Y¹ ═H; R¹═R² ═H/COOCH₂ H₅ ; R⁴ ═R⁵ ═CH₃), a tan solid melting over the range89°-144° C. Infrared maxima appeared at 1765 (C═O; s) and 1725 cm⁻¹(C═O; s). Analysis by mass spectrum showed m/e peaks at 524 (M⁺), 480(M⁺ --CO₂) and 451 (M⁺ --CO₂ C₂ H₅). A toluene solution of the productspotted on silica gel, an acidic clay or a phenolic resin developed aturquoise-colored image which had good lightfastness.

EXAMPLE 35

When α-bromotoluene was substituted for diethyl sulfate in Example 34for interaction with3-(2-methyl-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in Example 33, part A, there was obtained3-(2-methyl-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-phenylmethoxycarbonylphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R°═R³ ═Y¹ ═H; R¹ ═R² ═H/COOCH₂ C₆ H₅ ; R⁴═R⁵ ═CH₃), a light yellow solid melting over the range 92°-98° C.Infrared maxima appeared at 1765 (C═O; s) and 1725 cm⁻¹ (C═O; s).Analysis by mass spectrum showed m/e peaks at 586 (M³⁰ ) and 542(M+--CO₂). A toluene solution of the product spotted on silica gel, anacidic clay or a phenolic resin developed a turquoise-colored imagehaving good lightfastness.

EXAMPLE 36

A. Following a procedure similar to that described in part A of Example22, but using N,N-di-n-butylaniline instead of N,N-diethyl-m-phenetidinefor interaction with4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, therewas obtained3-(4-di-n-butylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula III: R═CH₂ (CH₂)₂ CH₃ ; R°═R³ ═R⁴ ═Y¹ ═H; R¹ ═R² ═H/COOH; R⁵═CH₃ ; R⁶ ═C₂ H₅), as a blue-colored solid melting over the range81°-94° C. Infrared maxima appeared at 1760 (C═O; s) and 1725 cm⁻¹ (C═O;m).

B. Employing a procedure similar to that described in part C of Example18 but using3-(4-di-n-butylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in part A above instead of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalidefor interaction with dimethyl sulfate, there was obtained3-(4-di-n-butylaminophenyl)-3-(1-ethyl2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide(Formula III: R═CH₂ (CH₂)₂ CH₃ ; R°═R³ ═R⁴ ═Y¹ ═H; R¹ ═R² ═H/COOCH₃ ; R⁵═CH₃ ; R⁶ ═C₂ H₅), a light yellow solid melting over the range 72°-94°C. Infrared maxima appeared at 1765 (C═O; s) and 1728 cm⁻¹ (C═O; s).Analysis by mass spectrum showed m/e peaks at 552 (M⁺), 508 (M⁺ --CO₂)and 493 (M⁺ --CO₂ CH₃). A toluene solution of the product spotted onsilica gel, an acidic clay or a phenolic resin developed a blue-coloredimage which had good lightfastness.

EXAMPLE 37

A. Following a procedure similar to that described in part A of Example22, but using N,N-dimethyl-m-anisidine instead ofN,N-diethyl-m-phenetidine for interaction with4/5carboxy-2-[(1ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, therewas obtained3-(2-methoxy-4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula III: R═R⁵ ═CH₃ ; R°═R³ ═Y¹ ═H; R¹ ═R² ═H/COOH; R⁴ ═OCH₃ ; R⁶═C₂ H₅), a deep blue solid melting over the range 128°-133° C. Infraredmaxima appeared at 1760 (C═O; s) and 1730 cm⁻¹ (C═O; m). Analysis bymass spectrum showed m/e peaks at 484 (M⁺), 440 (M⁺ --CO₂) and 439 (M⁺--COOH).

B. Employing a procedure similar to that described in part C of Example18, but using3-(2-methoxy-4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in part A above instead of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6carboxyphthalidefor interaction with dimethyl sulfate, there was obtained2-(2-methoxy-4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide(Formula III: R═R⁵ ═CH₃ ; R°═R³ ═Y¹ ═H; R¹ ═R² ═H/COOCH₃ ; R⁴ ═OCH₃ ; R⁶═C₂ H₅), as a light blue solid melting over the range 131°-135° C.Infrared maxima appeared at 1760 (C═0; s) and 1730 cm⁻¹ (C═O; s).Analysis by mass spectrum showed m/e peaks at 498 (M⁺), 454 (M⁺ --CO₂)and 439 (M⁺ --CO₂ CH₃). A toluene solution of the product spotted onsilica gel, an acidic clay or a phenolic resin developed a deepblue-colored image which had good lightfastness.

EXAMPLE 38

A. Proceeding in a manner similar to that described in part A of Example22, but using 3-n-butoxy-N,N-diethylaniline instead ofN,N-diethyl-m-phenetidine for interaction with4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, therewas obtained3-(2-n-butoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R°═R³ ═Y¹ ═H; R¹ ═R² ═H/COOH; R⁴ OCH₂ (CH₂)₂CH₃ ; R⁵ ═CH₃), a deep blue solid melting over the range 113°-125° C.Infrared maxima appeared at 1760 (C═O; s) and 1725 cm⁻¹ (C═O; m).Analysis by mass spectrum showed a m/e peak at 510 (M^(+--CO) ₂).

B. Following a procedure similar to that described in part C of Example18, but using3-(2-n-butoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in part A above instead of3-[2,4-bis(dimethylamino)-phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6carboxyphthalidefor interaction with dimethyl sulfate, there was obtained3-(2-n-butoxyl-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide(Formula III: R═R⁶ ═C₂ H₅ ; R°═R³ ═Y¹ ═H; R¹ ═R² ═H/COOCH₃ ; R⁴ OCH₂(CH₂)₂ CH₃ ; R⁵ CH₃), a light green oil. Infrared maxima appeared at1765 (C═O; s) and 1730 cm⁻¹ (C═O; s). A toluene solution of the productspotted on silica gel, an acidic clay or a phenolic resin developed adeep blue-colored image which had good lightfastness.

EXAMPLE 39

A. A stirred mixture of 19.2 g (0.10 mole) of trimellitic anhydride, 35g (0.22 mole) of 1-ethyl-2-methylindole and 75 ml of acetic anhydridewas heated at reflux for approximately one hour, then cooled slightlybelow reflux after which there was slowly added 100 ml of methanol. Theresulting solution was cooled to ambient temperature and slowly pouredwith stirring into a mixture of ice and water. The solid that formed wascollected by filtration and dried in vacuo at 60° C. to obtain3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide (Formula VI: R¹═R² ═H/COOH; R⁵ ═R^(5') ═CH₃ ; R⁶ ═R^(6') ═CH₂ CH₃ ; R°═R³ ═Y¹ ═Y^(1')═H), as a deep red solid melting over the range of 110°-119° C. Infraredmaxima appeared at 1760 (C═O; s) and 1720 cm⁻¹ (C═O; m). The nuclearmagnetic resonance spectrum was in accord with the assigned structure.

B. Following a procedure similar to that described above in part C ofExample 18, but using3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide prepared asdescribed above in part A of this example instead of3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalidefor interaction with dimethyl sulfate, there was obtained3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide(Formula VI: R¹ ═R² ═H/COOCH₃ ; R°═R³ ═Y¹ ═Y¹ ' ═H; R⁵ ═R^(5') ═CH₃ ; R⁶═R^(6') ═CH₂ CH₃), a tan solid melting over the range of 226°-229° C.with decomposition. Infrared maxima appeared at 1765 (C═O; s) and 1735cm⁻¹ (C═O; s). The nuclear magnetic resonance spectrum was concordantwith the assigned structure. Mass spectrum analysis showed m/e peaks at506 (M⁺), 462 (M⁺ --CO₂) and 447 (M⁺ --CO₂ CH₃). An acetone solution ofthe product spotted on silica gel, an acidic clay or a phenolic resindeveloped a deep red-colored image which had good xerographiccopiability and good lightfastness.

EXAMPLE 40

A stirred mixture of 3.0 g (0.006 mole) of3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalideprepared as in Example 39, part B and 35 ml of3-(di-n-butylamino)propylamine was heated at 125°-130° C. forapproximately five hours and then allowed to cool to ambienttemperature. The brown solution was poured into a mixture of water andtoluene and the toluene layer was separated, washed with water andconcentrated under reduced pressure. The excess amine was removed byvacuum distillation. There was thus obtained3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-(3-N,N-di-n-butylamino)propylaminocarbonylphthalide(Formula VI: R¹ ═R² ═H/CONH(CH₂)₃ N(n-C₄ H₉)₂ ; R⁵ ═R^(5') ═CH₃ ; R⁶═R^(6') ═C₂ H₅ ; R°═R³ ═Y¹ ═Y^(1') ═H), as a light brown oil. Infraredmaxima appeared at 1770 (C═O; s and 1650 cm⁻¹ (C═O; s). The nuclearresonance spectrum was concordant with the assigned structure. When asoy oil solution of the product was spotted on silica gel, an acidicclay or a phenolic resin, a dark red-colored image developed which hadgood lightfastness.

EXAMPLE 41

A. Following a procedure similar to that described in Example 18, part Babove, for interacting 10.6 g of4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid,prepared as described in Example 18, part A, and 7.0 g of1-n-butyl-2-methylindole, there was obtained 16 g of3-(1-ethyl-2-methyl-3-indolyl)-3-(1-n-butyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula VI: R¹ ═R² ═H/COOH; R⁵ ═R^(5') ═CH₃ ; R⁶ ═C₂ H₅ ; R^(6') ═n-C₄H₉ ; R°═R³ ═Y¹ ═Y^(1') ═H), a deep red solid melting over the range of128°-138° C. with decomposition. Infrared maxima appeared at 1762 (C═O;s) and 1738 cm⁻¹ (C═O; s).

B. Employing a procedure similar to that described above in part B ofExample 39, except that3-(1-ethyl-2-methyl-3-indolyl)-3-(1-n-butyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described above in part A of this example was used in placeof 3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide, there wasobtained3-(1-ethyl-2-methyl-3-indolyl)-3-(1-n-butyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide(Formula VI: R¹ ═R² ═H/COOCH₃ ; R⁵ ═R^(5') ═CH₃ ; R⁶ ═C₂ H₅ ; R^(6')═n-C₄ H₉ ; R°═R³ ═Y¹ ═Y^(1') ═H), a light orange solid melting over therange of 82°-94° C. Significant infrared maxima appeared at 1765 (C═O;s) and 1730 cm⁻¹ (C═O; s). Mass spectral analysis showed m/e peaks at534 (M⁺) and 490 (M⁺ --CO₂). A toluene solution of the product spottedon silica gel, an acidic clay or a phenolic resin developed a deepred-colored image which possessed good lightfastness.

EXAMPLE 42

A. Proceeding in a manner similar to that described in Example 41, partA above, but using 1-allyl-2-methylindole instead of1-n-butyl-2-methylindole for interaction with4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, therewas obtained3-(1-ethyl-2-methyl-3-indolyl)-3-(1-allyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula VI: R¹ ═R² ═H/COOH; R⁵ ═R^(5') ═CH₃ ; R⁶ ═C₂ H₅ ; R^(6') ═CH₂--CH═CH₂ ; R°═R³ ═Y¹ ═Y^(1') ═H), a deep red solid melting at 135° C.with decomposition. Significant infrared maxima appeared at 1765 (C═O;s) and 1730 cm⁻¹ (C═O; m).

B. When3-(1-ethyl-2-methyl-3-indolyl)-3-(1-allyl-2-methyl-3-indolyl)-5/6-carboxyphthalideprepared as described in part A of this example was substituted for3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide in theprocedure described in part B of Example 39, there was obtained3-(1-ethyl-2-methyl-3-indolyl)-3-(1-allyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide(Formula VI: R¹ ═R² ═H/COOH; R⁵ ═R^(5') ═CH₃ ; R⁶ ═C₂ H₅ ; R^(6') ═CH₂--CH═CH₂ ; R°═R³ ═Y¹ ═Y^(1') ═H), an orange solid melting over the rangeof 152°-164° C. Infrared spectral analysis showed maxima at 1760 (C═O;s) and 1732 cm⁻¹ (C═O; s). Nuclear magnetic resonance analysis was inaccord with the assigned structure. Analysis by mass spectrum showed m/epeaks at 518 (M⁺), 474 (M⁺ --CO₂) and 459 (M⁺ --COOCH₃). A toluenesolution of the product spotted on silica gel, and acid clay or aphenolic resin developed a deep red-colored image which had goodlightfastness.

EXAMPLE 43

Employing a procedure similar to that described in Example 18, part Babove, for interacting4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid,prepared as described in Example 18, part A and 1-ethyl-2-methylindole,there was obtained3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide (Formula VI: R¹═R² ═H/COOH; R⁵ ═R^(5') ═CH₃ ; R⁶ ═R^(6') ═CH₂ CH₃ ; R°═R³ ═Y¹ ═Y^(1')═H). Proceeding in a manner similar to that described in Example 39,part B, the following esters of the thus prepared3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide of Formula VI(R°═R³ ═Y¹ ═Y^(1') ═H; R⁵ ═R^(5') ═CH₃ ; R⁶ ═R^(6') ═CH₂ CH₃ ; R¹ /R²═H/COOH) above were prepared by esterification employing the appropriatedialkyl sulfate or organic halide. A toluene solution of theseindividual esters, when spotted on silica gel, an acidic clay or aphenolic resin, each developed a deep red-colored image which had goodlightfastness. The infrared analyses, nuclear magnetic resonanceanalyses and mass spectral analyses obtained for the products ofExamples 44 to 48 inclusive were concordant for the assigned structuregiven in those examples.

EXAMPLE 44

3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-ethoxycarbonylphthalide (FormulaVI: R¹ ═R² ═H/COOC₂ H₅ ; R⁵ ═R^(5') ═CH₃ ; R⁶ ═R^(6') ═CH₂ CH₃ ; R°═R³═Y¹ ═Y^(1') ═H) was obtained as a pale yellow solid melting over therange of 176°-179° C.

EXAMPLE 45

3,3-Bis(1-ethyl-2-methyl-3-indolyl)-5/6-n-butoxycarbonylphthalide(Formula VI: R¹ ═R² ═H/COO(CH₂)₃ CH₃ ; R⁵ ═R^(5') ═CH₃ ; R⁶ ═R^(6') ═CH₂CH₃ ; R°═R³ ═Y¹ ═Y^(1') ═H) was obtained as a light orange solid meltingat 88° C. with decomposition.

EXAMPLE 46

3,3-Bis(1-ethyl-2-methyl-3-indolyl)-5/6-n-octyloxycarbonylphthalide(Formula VI: R¹ ═R² ═H/COO(CH₂)₇ CH₃ ; R⁵ ═R^(5') ═CH₃ ; R⁶ ═R^(6') ═CH₂CH₃ ; R°═R³ ═Y¹ ═Y^(1') ═H) was obtained as an orange oil.

EXAMPLE 47

3,3-Bis(1-ethyl-2-methyl-3-indolyl)-5/6-phenylmethoxycarbonylphthalide(Formula VI: R¹ ═R² ═H/COOCH₂ C₆ H₅ ; R⁵ ═R^(5') ═CH₃ ; R⁶ ═R^(6') ═CH₂CH₃ ; R°═R³ ═Y¹ ═Y^(1') ═H) was obtained as a light orange solid meltingover the range of 94°-100° C. with decomposition.

EXAMPLE 48

3,3-Bis(1-ethyl-2-methyl-3-indolyl)-5/6-allyloxycarbonylphthalide(Formula VI: R¹ ═R² --H/COOCH₂ CH═CH₂ ; R⁵ ═R^(5') ═CH₃ ; R⁶ ═R^(6')═CH₂ CH₃ ; R°═R³ ═Y¹ ═Y^(1') ═H) was obtained as a light orange solidmelting over the range of 75°-87° C.

EXAMPLE 49

3,3-Bis(1-ethyl-2-methyl-3-indolyl)-5/6-n-hexadecyloxycarbonylphthalide(Formula VI: R¹ ═R² --H/COO(CH₂)₁₅ CH₃ ; R⁵ ═R^(5') ═CH₃ ; R⁶ ═R^(6')═CH₂ CH₃ ; R°═R³ ═Y¹ ═Y^(1') ═H) was obtained as a dark red oil.Infrared maxima appeared at 1770 (C═O; s) and 1730 cm⁻¹ (C═O; s).

EXAMPLE 50

Proceeding in a manner similar to that described in Example 13 above,4.43 g (0.01 mole) of2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]-3,4,5,6-tetrachlorobenzoicacid, prepared as described in Example 2, part A above, was interactedwith 2.0 g (0.015 mole) of m-amino-N,N-dimethylaniline in the presenceof ten ml of acetic anhydride to obtain3-[2-acetamido-4-dimethylaminophenyl]-3-(1-ethyl-2-methyl-3-indolyl)-3,5,6,7-tetrachlorophthalide(Formula III: R°═R¹ ═R² ═R³ ═Cl; R═R⁵ ═CH₃ ; ##STR28## R⁶ ═CH₂ CH₃ ; Y¹═H) which developed a blue-green color when spotted on silica gel in theform of a toluene solution.

EXAMPLE 51

Following a procedure similar to that described in part B of Example 2above, 4.45 g (0.01 mole) of2-(1-ethyl-2-methyl-3-indolyl)carbonyl-3,4,5,6-tetrachlorobenzoic acidand 2.20 g (0.01 mole) of N,N,N',N'-tetraethyl-m-phenylenediamine wereinteracted in the presence of ten ml of acetic anhydride to obtain3-[2,4-bis(diethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-4,5,6,7-tetrachlorophthalide(Formula III: R°═R¹ ═R² ═R³ ═Cl; R═R⁶ ═CH₂ CH₃ ; R⁴ ═N(CH₂ CH₃)₂ ; R⁵═CH₃ ; Y¹ ═H) melting at 100°-103° C. and showing a significant infraredabsorption maxima at 1770 cm⁻¹ (C═O; s). A toluene solution of thiscompound developed an intense blue color when spotted on silica gel.

EXAMPLE 52

Employing a procedure similar to that described in part C of Example 1,9.72 g (0.04 mole) of 2-(1,2-dimethyl-3-indolyl)-carbonylbenzoic acidprepared as described in U.S. Pat. No. 3,509,173, 8.57 g (0.05 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine and 6.0 ml of acetic anhydrideare interacted to obtain3-[2,4-bis(dimethylamino)phenyl]-3-(1,2-dimethyl-3-indolylphthalide(Formula III: R°═R¹ ═R² ═R³ ═Y¹ ═H; R═R⁵ ═R⁶ ═CH₃ ; R⁴ ═N(CH₃)₂).

EXAMPLE 53

A. Employing a procedure similar to that described in part A of Example10 above, 7.15 g (0.025 mole) of tetrachlorophthalic anhydride and 3.65g (0.028 mole) of 2-methylindole were interacted in 100 ml of ethylenedichloride to obtain2-[(2-methyl-3-indolyl)carbonyl]-4,5,6,7-tetrachlorobenzoic acid(Formula VIII: R°═R¹ ═R² ═R³ ═Cl; R⁵ ═CH₃ ; R⁶ ═Y¹ ═H), an orange solidmelting at 200°-201° C.

B. A stirred mixture of 4.17 g of2-[(2-methyl-3-indolyl)carbonyl]-4,5,6,7-tetrachlorobenzoic acid,prepared as described in part A above and 3.28 g (0.02 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine were interacted in the presenceof 40 ml of acetic anhydride after the manner described in Example 2,part B above to obtain3-[2,4-bis(dimethylamino)phenyl]-3-(2-methyl-3-indolyl)-4,5,6,7-tetrachlorophthalide(Formula III: R°═R¹ ═R² ═R³ ═Cl; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂ ; R⁶ ═Y¹ ═H)which showed an infrared carbonyl absorption maximum at 1775 cm⁻¹. Atoluene solution of the compound developed a blue-black color whenspotted on silica gel.

EXAMPLE 54

Proceeding in a manner similar to that described in part B of Example 5above, 2.34 g (0.006 mole) of2-[(1-n-octyl-2-methyl-3-indolyl)carbonyl]benzoic acid preparedaccording to Example 5, part A, and 2.40 g ofN,N,N',N'-tetraethyl-m-phenylenediamine were interacted in the presenceof 2.40 g of acetic anhydride to obtain3-[2,4-bis(diethylamino)phenyl]-3-(1-n-octyl-2-methyl-3-indolyl)phthalide(Formula III: R°═R¹ ═R² ═R³ ═Y¹ ═H; R═CH₂ CH₃ ; R⁴ ═N(CH₂ CH₃)₂ ; R⁵═CH₃ ; R⁶ ═(CH₂)₇ CH₃) as a tar-like semisolid. A toluene solution ofthis material developed as purple color when spotted on silica gel.

EXAMPLE 55

A. Proceeding in a manner similar to that described in part A of Example10, 29.6 g (0.20 mole) of phthalic anhydride and 35.2 g (0.20 mole) of5-nitro-2-methylindole were interacted in 100 ml of ethylene dichlorideto obtain 2-[(2-methyl-5-nitro-3-indolyl)carbonyl]benzoic acid (FormulaVIII: R°═R¹ ═R² ═R³ ═R⁶ ═H; R⁵ ═CH₃ ; Y¹ ═5-NO₂), a red brown solidmelting at 144°-148° C. and showing a strong carbonyl absorption maximumat 1700 cm⁻¹ in the infrared spectrum.

B. Following a procedure similar to that described in part B of Example18 for interacting 3.24 g (0.01 mole) of2-[(2-methyl-5-nitro-3-indolyl)carbonyl]benzoic acid, prepared asdescribed in part A above, and 1.6 g (0.01 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine in the presence of 5.0 ml ofacetic anhydride, there is obtained3-[2,4-bis(dimethylamino)phenyl]-3-(2-methyl-5-nitro-3-indolyl)phthalide(Formula III: R°═R¹ ═R² ═R³ ═R⁶ ═H; R═R⁵ ═CH₃ ; R⁴ ═N(CH₃)₂ ; Y¹ ═NO₂).

EXAMPLE 56

A. Using a procedure similar to the one described in part A of Example18, 48.0 g (0.25 mole) of trimellitic anhydride and 32.8 g (0.25 mole)of 2-methylindole were interacted in 250 ml of ethylene dichloride toobtain 66.1 g of 4/5-carboxy-2-[(2-methyl-3-indolyl)carbonyl]benzoicacid (Formula VIII: R¹ ═R² ═H/COOH; R°═R³ ═R⁶ ═Y¹ ═H; R⁵ ═CH₃) meltingat 237°-241° C.

B. A procedure similar to that described in part B of Example 18 above,was followed for interacting 10 g (0.023 mole) of4/5-carboxy-2-[(2-methyl-3-indolyl)carbonyl]benzoic acid, prepared asdescribed in part A above, and 8.0 g (0.06 mole) of 2-methylindole inthe presence of 50 ml of acetic anhydride. There was thus obtained3,3-bis(2-methyl-3-indolyl)-5/6-carboxyphthalide (Formula VI: R¹ ═R²═H/COOH; R°═R³ ═R⁶ ═R^(6') ═Y¹ ═Y^(1') ═H; R⁵ ═R^(5') ═CH₃), a pinksolid melting over the range of 145°-165° C.

EXAMPLE 57

A. Proceeding in a similar fashion to the one described in part A ofExample 17, 28.6 g (0.01 mole) of tetrachlorophthalic anhydride, 16.2 g(0.2 mole) of N-methylpyrrole and 40 g (0.3 mole) of aluminum chloridewere interacted in 50 ml of dry chlorobenzene to obtain2-[(1-methyl-2-pyrrolyl)carbonyl]-3,4,5,6-tetrachlorobenzoic acid(Formula IX: R°═R¹ ═R² ═R³ ═Cl; R⁷ ═CH₃) having a melting point of203°-205° C.

B. Employing the procedure of part B of Example 17 hereinabove, 3.70 g(0.01 mole) of2-[(1-methyl-2-pyrrolyl)carbonyl]-3,4,5,6-tetrachlorobenzoic acid,prepared as described in part A above, and 2.0 g (0.012 mole) ofN,N,N',N'-tetramethyl-m-phenylenediamine were interacted in the presenceof 10 ml of acetic anhydride to obtain3-[(2,4-bis(dimethylamino)phenyl]-3-(1-methyl-2-pyrrolyl)-4,5,6,7-tetrachlorophthalide(Formula IV: R°═R¹ ═R² ═R³ ═Cl; R═R⁷ ═CH₃ ; R⁴ ═N(CH₃)₂).

EXAMPLE 58

To a stirred solution of 5.3 g of3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide,prepared as described in Example 22, part A, in 25 ml of acetone, therewas added 30 ml of a 0.5 N methanolic sodium hydroxide solution. Themixture was stirred for approximately fifteen minutes at ambienttemperature and concentrated to a syrup under vacuum. A small portion offresh acetone was added to the syrup and the dark blue crystals whichformed were collected by filtration. A small portion of hexane was addedto the crystals resulting in a gummy residue. The residue was thentriturated with more hexane to obtain a bright blue powder which wascollected by filtration and dried to yield 4.8 g of the sodium salt of3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide(Formula III: R°═R³ ═Y¹ ═H; R¹ ═R² ═H/COO⊖Na⊕; R═R⁶ ═C₂ H₅ ; R⁴ ═OC₂ H₅; R⁵ ═CH₃), a bright blue colored powder melting over the range 82°-95°C. Infrared spectral analysis showed significant maxima at 1752 (C═O, s)and 1735 cm⁻¹ (C═O, s).

It is contemplated that by following procedures similar to thosedescribed in the foregoing examples but employing appropriate 2-{[(1-R⁶-2-R⁵ -5/6-Y¹)-3-indolyl]carbonyl}-3-R°-4-R¹ -5-R² -6-R³ -benzoic acidsof Formula VIII and appropriately substituted 3-R⁴ -N,N-(R)₂ -anilinesthere will be obtained the 3-[2-R⁴ -4-N(R)₂ -phenyl]3-[(1-R⁶ -2-R⁵-5/6Y¹)-3-indolyl]-4-R°-5-R¹ -6-R² -7-R³ -phthalides of Formula III,Examples 59-75, presented in Table A hereinbelow.

                                      TABLE A                                     __________________________________________________________________________    Phthalides of Formula III                                                     __________________________________________________________________________    Ex.                                                                              R         R.sup.0                                                                         R.sup.1      R.sup.2      R.sup.3                              __________________________________________________________________________    59 n-C.sub.4 H.sub.9                                                                       H H            N(C.sub.2 H.sub.5).sub.2                                                                   H                                    60 C.sub.6 H.sub.5 CH.sub.2                                                                H H/COONHC.sub.8 H.sub.17                                                                    H/COONHC.sub.8 H.sub.17                                                                    H                                    61 C.sub.3 H.sub.7                                                                         H H            H            F                                    62 CH.sub.3  H H/COO-i-C.sub.3 H.sub.7                                                                    H/COO-i-C.sub.3 H.sub.7                                                                    H                                    63 4-Cl--C.sub.6 H.sub.4 CH.sub.2                                                          H H/COO.sup.⊖ K.sup.⊕                                                            H/COO.sup.⊖ K.sup.⊕                                                            H                                    64 i-C.sub.3 H.sub.7                                                                       H I            H            H                                    65 CH.sub.3  H Br           Br           H                                    66 4-CH.sub.3 --C.sub.6 H.sub.4 CH.sub.2                                                   H H/COON(C.sub.2 H.sub.5).sub.2                                                              H/COON(C.sub.2 H.sub.5).sub.2                                                              H                                    67 i-C.sub.4 H.sub.9                                                                       Br                                                                              Br           Br           Br                                   68 2-F--C.sub.6 H.sub.4 CH.sub.2                                                           H H/COO.sup.⊖ NH.sup.⊕.sub.4                                                     H/COO.sup.⊖ NH.sup.⊕.sub.4                                                     H                                    69 2,5(CH.sub.3).sub.2 C.sub.6 H.sub.3 CH.sub.2                                            H N(n-C.sub.4 H.sub.9).sub.2                                                                 H            H                                    70 C.sub.2 H.sub.5                                                                         H H/COON(CH.sub. 2).sub.8 --                                                                 H/COON(CH.sub.2).sub.8 --                                                                  H                                                   CH(CH.sub.3).sub.2                                                                         CH(CH.sub.3).sub.2                                71 C.sub.6 H.sub.4 CH.sub.2                                                                H H/COOCH.sub.2 C.sub.6 H.sub.4 Cl                                                           H/COOCH.sub.2 C.sub.6 H.sub.4 Cl                                                           H                                    72 CH.sub.3  H H/COONC.sub.6 H.sub.13                                                                     H/COONC.sub.6 H.sub.13                                                                     H                                    73 n-C.sub.4 H.sub.9                                                                       H H/COO.sup.⊖⊕ NHCH.sub.3 C.sub.14 H.sub.29                                      H/COO.sup.⊖⊕ NHCH.sub.3 C.sub.14                                  H.sub.29     H                                    74 C.sub.2 H.sub.5                                                                         H H/COOCH.sub.2 C.sub.6 H.sub.3 --                                                           H/COOCH.sub.2 C.sub.6 H.sub.3 --                                                           H                                                   (CH.sub.3).sub.2                                                                           (CH.sub.3).sub.2                                  75 C.sub.6 H.sub.5 CH.sub.2, CH.sub.3                                                      H H/COONHC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                   H/COONHC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                   H                                    __________________________________________________________________________                  Ex.                                                                              R.sup.4                                                                              R.sup.5                                                                          R.sup.6   Y.sup.1                                  __________________________________________________________________________                  59 N(n-C.sub.4 H.sub.9).sub.2                                                           C.sub.2 H.sub.5                                                                  H         5-CH.sub.3                                             60 OC.sub.3 H.sub.7                                                                     H  C.sub.6 H.sub.5 CH.sub.2                                                                5-F                                                    61 N(C.sub.3 H.sub.7).sub.2                                                             H  CH.sub.3  6-NO.sub.2                                             62 Cl     C.sub.2 H.sub.5                                                                  H         5,6-Cl.sub.2                                           63 C.sub.3 H.sub.7                                                                      CH.sub.3                                                                         2-CH.sub.3 -1-C.sub.3 H.sub.4                                                           H                                                      64 N(i-C.sub.3 H.sub.7)                                                                 CH.sub.3                                                                         2,6-(Cl).sub.2 C.sub.6 H.sub.3 CH.sub.2                                                 H                                                      65 N(CH.sub.3).sub.2                                                                    H  H         5,6(OCH.sub.3).sub.2                                   66 OC.sub.4 H.sub.9                                                                     H  i-C.sub.5 H.sub.11                                                                      H                                                      67 N(i-C.sub.4 H.sub.9).sub.2                                                           CH.sub.3                                                                         C.sub.2 H.sub.3                                                                         H                                                      68 Br     C.sub.2 H.sub.5                                                                  H         5-CH.sub.3                                             69 NHCOCH.sub.3                                                                         H  1-CH.sub.3 C.sub.6 H.sub.12                                                             5-I                                                    70 OCH.sub.3                                                                            C.sub.3 H.sub.7                                                                  H         H                                                      71 I      CH.sub.3                                                                         H         5,6(CH.sub.3).sub.2                                    72 O-i-C.sub.3 H.sub.7                                                                  CH.sub.3                                                                         H         6-Br                                                   73 C.sub.2 H.sub.5                                                                      CH.sub.3                                                                         2-F-C.sub.6 H.sub.4 CH.sub.2                                                            H                                                      74 OC.sub.4 H.sub.9                                                                     H  CH.sub.3  5-Br-6-NO.sub.2                                        75 C.sub.2 H.sub.5                                                                      CH.sub.3                                                                         C.sub.2 H.sub.5                                                                         H                                        __________________________________________________________________________

It is contemplated that by following precedures similar to thosedescribed in the foregoing examples but employing the appropriate2-(1-R⁷ -2-pyrrolyl)carbonyl-3-R°-4-R¹ -5-R² -6-R³ -benzoic acids ofFormula IX and appropriately substituted 3-R⁴ -N,N-(R)₂ -anilines therewill be obtained the 3-[2-R⁴ -4-N(R)₂ -phenyl]-3-(1-R⁷-2-pyrrolyl)-4-R°-5-R¹ -6-R² -7-R³ -phthalides of Formula IV, Examples76-87, presented in Table B hereinbelow.

                                      TABLE B                                     __________________________________________________________________________    Phthalides of Formula IV                                                      Ex.                                                                              R         R.sup.0                                                                         R.sup.1     R.sup.2     R.sup.3                                                                         R.sup.4                                                                             R.sup.7                        __________________________________________________________________________    76 n-C.sub.4 H.sub.9                                                                       H H           N(C.sub.2 H.sub.5).sub.2                                                                  H N(n-C.sub.4 H.sub.9).sub.2                                                          C.sub.6 H.sub.5                77 2,4-Cl.sub.2 --C.sub.6 H.sub.3 CH.sub.2                                                 H H/COO.sup.⊖ Li.sup.⊕                                                          H/COO.sup.⊖ Li.sup.⊕                                                          H OC.sub.4 H.sub.9                                                                    C.sub.2 H.sub.5                78 C.sub.2 H.sub.5                                                                         H Br          H           H N(C.sub.2 H.sub.5).sub.2                                                            i-C.sub.3 H.sub.7              79 i-C.sub.3 H.sub.7                                                                       Br                                                                              Br          Br          Br                                                                              N(i-C.sub.3 H.sub.7).sub.2                                                          C.sub.2 H.sub.5                80 4-BrC.sub.6 H.sub.4 CH.sub.2                                                            H H/COOC.sub.10 H.sub.21                                                                    H/COOC.sub.10 H.sub.21                                                                    H Cl    CH.sub.3                       81 2-F-C.sub.6 H.sub.4 CH.sub.2                                                            H H/COONHC.sub.12 H.sub.23                                                                  H/COONHC.sub.12 H.sub.23                                                                  H OCH.sub.3                                                                           n-C.sub.3 H.sub.7              82 2,5-(CH.sub.3).sub.2 C.sub.6 H.sub.3 CH.sub.2                                           H H/COON(n-C.sub.4 H.sub.9).sub.2                                                           H/COON(n-C.sub.4 H.sub.9).sub.                                                            H I     C.sub.6 H.sub.5                83 C.sub.6 H.sub.5 CH.sub.2, s-C.sub.4 H.sub.9                                             H H/COO.sup.⊖⊕ NH.sub.3 C.sub.18 H.sub.37                                       H/COO.sup.⊖⊕ NH.sub.3 C.sub.18                                    H.sub.37    H C.sub.3 H.sub.7                                                                     C.sub.2 H.sub.5                84 C.sub.2 H.sub.5                                                                         Cl                                                                              Cl          Cl          Cl                                                                              N(C.sub.2 H.sub.5).sub.2                                                            i-C.sub.3 H.sub.7              85 C.sub.6 H.sub.4 CH.sub.2                                                                H NO.sub.2    H           H NHCOCH.sub.3                                                                        C.sub.6 H.sub.5                86 n-C.sub.3 H.sub.7                                                                       H NHCOCH.sub.3                                                                              H           H Br    C.sub.2 H.sub.5                87 CH.sub.3  H H/COONHC.sub.2 H.sub.4 --                                                                 H/COONHC.sub.2 H.sub.4 --                                                                 H CH.sub.3                                                                            CH.sub.3                                      N(i-C.sub.3 H.sub.7).sub.2                                                                N(i-C.sub.3 H.sub.7).sub.2                         __________________________________________________________________________

It is contemplated that by following procedures similar to thosedescribed in the foregoing examples but employing the appropriate2-(9-R⁸ -3-carbazolyl)carbonyl-3-R°-4-R¹ -5-R² -6-R³ -benzoic acids andappropriately substituted 3-R⁴ -N,N-(R)₂ -anilines there will beobtained the 3-[2-R⁴ -4-N(R)₂ -phenyl]-3-(9-R⁸ -3-carbazolyl)-4-R°-5-R¹-6-R² -7-R³ -phthalides of Formula V, Examples 88-98, presented in TableC hereinbelow.

                                      TABLE C                                     __________________________________________________________________________    Phthalides of Formula V                                                       Ex.                                                                              R         R.sup.0                                                                         R.sup.1      R.sup.2      R.sup.3                                                                         R.sup.4                                                                             R.sup.8                      __________________________________________________________________________    88 C.sub.6 H.sub.5 CH.sub.2                                                                H H/COOH       H/COOH       H Cl    i-C.sub.3 H.sub.7            89 n-C.sub.3 H.sub.7                                                                       Cl                                                                              Cl           H            Cl                                                                              N(n-C.sub.3 H.sub.7).sub.2                                                          C.sub.6 H.sub.5              90 C.sub.6 H.sub.5 CH.sub.2,C.sub.2 H.sub.5                                                H H/COO-n-C.sub.4 H.sub.9                                                                    H/COO-n-C.sub.4 H.sub.9                                                                    H H     C.sub.2 H.sub.5              91 3-Cl--C.sub.6 H.sub.4 CH.sub.2                                                          H H/COO.sup.⊖ Na.sup.⊕                                                           H/COO.sup.⊖ Na.sup.⊕                                                           H I     n-C.sub.3 H.sub.7            92 i-C.sub.4 H.sub.9                                                                       H H/COONHC.sub.16 H.sub.33                                                                   H/COONHC.sub.16 H.sub.33                                                                   H NHCOCH.sub.3                                                                        CH.sub.3                     93 C.sub.2 H.sub.5                                                                         Br                                                                              Br           Br           Br                                                                              N(C.sub.2 H.sub.5).sub.2                                                            i-C.sub.3 H.sub.7            94 2,5-(CH.sub.3).sub.2 C.sub.6 H.sub.3 CH.sub.2                                           H H/COOC.sub.2 H.sub.3                                                                       H/COOC.sub.2 H.sub.3                                                                       H o-i-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5              95 2-F--C.sub.6 H.sub.4 CH.sub.2                                                           H H/COO.sup.⊖ ⊕ NH.sub.3 C.sub.6 H.sub.13                                        H/COO.sup.⊖ ⊕ NH.sub.3 C.sub.6                                    H.sub.13     H Br    C.sub.2 H.sub.5              96 2,6-Cl.sub.2 C.sub.6 H.sub.3 CH.sub.2                                                   H H/COON(C.sub.18 H.sub.37).sub.2                                                            H/COON(C.sub.18 H.sub.37).sub.2                                                            H C.sub.3 H.sub.7                                                                     i-C.sub.3 H.sub.7            97 4-Cl--C.sub.6 H.sub.8 CH.sub.2                                                          H H/COOC.sub.12 H.sub.25                                                                     H/COOC.sub.12 H.sub.25                                                                     H Cl    CH.sub.3                     98 n-C.sub.3 H.sub.7                                                                       H H/COONHC.sub.3 H.sub.7 N(CH.sub.3).sub.2                                                   H/COONHC.sub.3 H.sub.7 N(CH.sub.3).sub.2                                                   H CH.sub.3                                                                            C.sub.6 H.sub.5              __________________________________________________________________________

It is contemplated that by following procedures similar to thosedescribed in the foregoing examples but employing the appropriate2-{[(1-R⁶ -2-R⁵ -5/6-Y¹)-3-indolyl[carbonyl}-3-R°-4-R¹ -5-R² -6-R³-benzoic acids of Formula VIII and appropriately substituted 1-R^(6')-2-R^(5') -5/6-Y^(1') -indoles there will be obtained the 3-[(1-R⁶ -2-R⁵-5/6-Y¹)-3-indolyl]-3-[(1-R^(6') -2-R^(5')-5/6-Y^(1'))-3-indolyl[-4-R°-5-R¹ -6-R² -7-R³ -phthalides of Formula VI,Examples 99-112, presented in the Table D hereinbelow.

                                      TABLE D                                     __________________________________________________________________________    Phthalides of Formula VI                                                      Ex.                                                                              R.sup.o                                                                         R.sup.1 /R.sup.2                                                                           R.sup.3                                                                         R.sup.5                                                                           R.sup.6  Y.sup.1                                                                             R.sup.5'                                                                         R.sup.6'  Y.sup.1'                  __________________________________________________________________________     99                                                                              H H/COO.sup.⊖ K.sup.⊕                                                            H H   H        H     H  C.sub.4 H.sub.9                                                                         OCH.sub.3                 100                                                                              H H/COOC.sub.18 H.sub.37                                                                     H H   C.sub.6 H.sub.4 CH.sub.2                                                               5-F   C.sub.6 H.sub.5                                                                  H         H                         101                                                                              H H/COONHC.sub.6 H.sub.13                                                                    H H   CH.sub.3 6-NO.sub.2                                                                          C.sub.2 H.sub.5                                                                  H         CH.sub.3                  102                                                                              H H/COO.sup.⊖⊕ NH(CH.sub.3).sub.3                                                H i-C.sub.3 H.sub.7                                                                 H        H     H  CH.sub.3  5-Br,6-NO.sub.2           103                                                                              H H/COONH.sub.2                                                                              H CH.sub.3                                                                          H        6-Br  CH.sub.3                                                                         2,5-(CH.sub.3).sub.2 C.sub.6                                                  H.sub.3 CH.sub.2                                                                        H                         104                                                                              H H/COOC.sub.14 H.sub.29                                                                     H CH.sub.3                                                                          2-(C.sub.2 H.sub.5)C.sub.6 H.sub.12                                                    H     CH.sub.3                                                                         C.sub.2 H.sub.3                                                                         H                         105                                                                              H H/COON(CH.sub.3).sub.2                                                                     H i-C.sub.3 H.sub.7                                                                 4-BrC.sub.6 H.sub.4 CH.sub.2                                                           H     H  H         5,6-(CH.sub.3).sub.                                                           2                         106                                                                              H H/COO(CH.sub.2).sub.8 CH(CH.sub.3).sub.2                                                   H H   i-C.sub.5 H.sub.11                                                                     H     C.sub.6 H.sub.5                                                                  H         5,6-(Cl).sub.2            107                                                                              H H/COO.sup.⊖⊕ NH.sub.4                                                          H CH.sub.3                                                                          2-CH.sub.3 --C.sub.6 H.sub.4 CH.sub.2                                                  H     H  1-CH.sub.3 -C.sub.6 H.sub.12                                                            5-I                       108                                                                              H H/COOCH.sub.2 C.sub.6 H.sub.4 Cl                                                           H CH.sub.3                                                                          3-(2-CH.sub.3)-1-C.sub.3 H.sub.3                                                       H     CH.sub.3                                                                         2,5-(CH.sub.3).sub.2 C.sub.6                                                  H.sub.3 CH.sub.2                                                                        H                         109                                                                              H H/COOCH.sub.2 C.sub.6 H.sub.3 (CH.sub.3).sub.2                                             H CH.sub.3                                                                          i-C.sub.4 H.sub.9                                                                      H     CH.sub.3                                                                         C.sub.18 H.sub.37                                                                       H                         110                                                                              H H/COO[3-(2-CH.sub.3)-1C.sub.3 H.sub.3 ]                                                    H CH.sub.3                                                                          H        5,6-(CH.sub.3).sub.2                                                                C.sub.2 H.sub.5                                                                  3-Cl--C.sub.6 H.sub.4 CH.sub.2                                                          H                         111                                                                              H H/COOC.sub.6 H.sub.13                                                                      H CH.sub.3                                                                          2-F--C.sub.6 H.sub.4 CH.sub.2                                                          H     CH.sub.3                                                                         CH.sub.3  6-NO.sub.2                112                                                                              H H/COONHC.sub.6 H.sub.12 N(CH.sub.3).sub.2                                                  H C.sub.2 H.sub.5                                                                   H        CH.sub.3                                                                            CH.sub.3                                                                         C.sub.2 H.sub.5                                                                         H                         __________________________________________________________________________

EXAMPLE 113

The use of the compounds of Formulas I through VI and described inExamples 1 through 112 as color forming components in pressure sensitivemicroencapsulated copying systems is illustrated with reference to theproduct of Example 1, part B.

A. A mixture of 196 ml of distilled water and 15.0 g of pigskin gelatinwas stirred at approximately 50° C. for approximately 45 minutes. Therewas then added to the mixture a warmed (approximately 50° C.) solutionof 49.0 g of alkylated biphenyls and 0.5 g of3-[2,4-bis(diethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)phthalide,prepared as described above in Example 1, part B. The resulting solutionwas stirred for approximately fifteen minutes. A second solution of 81.0ml of distilled water and 10.0 g of gum arabic was then prepared andwarmed to approximately 50° C. for approximately one hour.

B. The two solutions, the first containing water, gelatin, alkylatedbiphenyls and the product, and the second containing water and gumarabic were mixed and the pH adjusted to 9 by the addition ofapproximately 0.7 ml of 20 percent aqueous sodium hydroxide. Theresulting mixture was transferred to a larger reactor equipped with avariable speed one-half horsepower Eppenbach Homo-Mixer (Gifford-WoodCo., Hudson, N.Y.) and there was added over a period of two to threeminutes 650 ml of distilled water which had been heated to 50° C. Withthe stirrer running at an applied voltage of between 20 to 25 voltsthere was slowly added sufficient ten percent aqueous acetic acid to setthe pH at 4.5, this being the point where coacervation was initiated.The stirrer speed was increased by raising the applied voltage toapproximately thirty volts and approximately four drops of2-ethylhexanol were added to suppress foaming. After approximatelytwenty minutes, a sample of the suspension was examined microscopicallyand found to have stabilized in the range of 20 to 25 microns particlesize whreupon an external ice/water bath was immediately placed aroundthe reactor containing the suspension. At approximately 20° C., theagitation speed was reduced by decreasing the applied voltage to therange of 20 to 25 volts. Cooling was continued and at approximately 15°C., 10.0 ml of glutaraldehyde was added over a period of five minutes.When the internal temperature reached 10° C., the agitation speed wasfurther reduced by lowering the applied voltage to approximately 20volts and these conditions maintained for approximately thirty minutes.At this time, the Eppenbach Homo-Mixer was replaced with a conventionalblade type laboratory agitator and the suspension was stirred anadditional three hours during which period the temperature was allowedto warm to room temperature. The microencapsulated product was isolatedby pouring the slurry through an ASTM #18 stainless steel sieve toremove any large agglomerates and then collecting the capsules byfiltration. The collected capsules were washed successively with four100 ml portions of distilled water each and stored as a water wet pulp.A sample of the pulp analyzed by drying in vacuo at 80° C. was found toconsist of 37.5 percent solids.

C. To 125 ml of distilled water, 10.6 g of oxidized corn starch wasadded over a period of ten to fifteen minutes with stirring. Thismixture was heated to a temperature in the range of 70°-80° C. andmaintained until all the starch dissolved. The starch solution wascooled to ambient temperature and there was added 100 g of thecapsule-containing water wet pulp from part B above and 43.0 ml ofdistilled water. The capsules and starch solution were mixed at roomtemperature using an Eppenbach Homo-Mixer set at an applied voltage of25 volts for five minutes and then at an applied voltage of 30 volts foran additional five minutes to complete the suspension of the capsules inthe starch solution.

D. The stock starch-microcapsule suspension prepared in part C above wascoated on paper sheets to a thicknes of approximately 0.0015 inch andthe coated paper air dried. The paper thus coated with themicroencapsulated colorless precursor was assembled as the top sheet ina manifold system by positioning the coated side in contact with thecoated side of a commercially available receiving sheet coated with acolor developer of the electron accepting type. More specifically,papers coated with a phenolic resin and with an acidic clay wereemployed in this test. An image was then drawn with a stylus on the topsheet bearing the microencapsulated colorless precursor on its reverseside causing the affected microcapsules to rupture thus allowing thesolution of the colorless precursor held by said microcapsules to flowinto contact with the color developing substance on the receiving sheetwhereupon a deep blue-colored image promptly formed. The developed imageexhibited good lightfastness when exposed to daylight or to a dayligntfluorescent lamp for extended periods.

When evaluated in a duplicating system prepared and tested as describedabove, the product of Example 1, part C,3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2l-methyl-3-indolyl)-phthalide produced a grape-colored developed image.

EXAMPLE 114

The use of the compounds of Formulas I through VI and described inExamples 1 through 112 as color forming components in pressure sensitivemicroencapsulated copying systems is similarly illustrated withreference to the product of Example 23.

A. A mixture of 196 ml of distilled water and 15.0 g of pigskin gelatinwas stirred at approximately 50° C. for approximately 45 minutes. Therewas then added to the mixture a warmed (approximately 50° C.) solutionof 49.0 g of alkylated biphenyls and 1.0 g of3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-ethoxycarbonylphthalideprepared as described above the Example 23. The resulting solution wasstirred for approximately fifteen minutes. A second solution of 81.0 mlof distilled water and 5.0 g of carboxymethylcellulose was then preparedand warmed to approximately 50° C. for approximately one hour.

B. The two solutions, the first containing water, gelatin, alkylatedbiphenyls and the product, and the second containing water withcarboxymethylcellulose were mixed by means of an Eppenbach Homo-Mixer(Gifford-Wood Co., Hudson, N.Y.). The pH was adjusted to 6.5 by theaddition of approximately 0.7 ml of 20 percent aqueous sodium hydroxide.To the resultant mixture was added over a period of two to three minutes650 ml of distilled water which had been heated to 50° C. With thestirrer running at an applied voltage of between 35 to 40 volts therewas slowly added sufficient ten percent aqueous acetic acid to set thepH at 4.5, this being the point where coacervation was initiated. Fourdrops of 2-ethylhexanol were added to suppress foaming. Afterapproximately twenty minutes an external ice/water bath was placedaround the reactor containing the suspension. Cooling was continued andat approximately 15° C., 10.0 ml of glutaraldehyde was added over aperiod of five minutes. When the internal temperature reached 10° C.,the Eppenbach Homo-MIxer was replaced with a conventional blade typelaboratory agitator and the thus prepared suspension of microcapsuleswas stirred an additional three hours during which period thetemperature was allowed to warm to room temperature.

C. The microcapsule suspension prepared as described in part B above wascoated on paper sheets to a thickness of approximately 0.0015 inch andthe coated paper air dried. The paper thus coated with themicroencapsulated colorless precursor was assembled as the top sheet ina manifold system by positioning the coated side in contact with thecoated side of a commercially available receiving sheet coated with acolor developer of the electron accepting type. More specifically,papers coated with a phenolic resin and with an acidic clay wereemployed in this test. An image was then drawn with a stylus on the topsheet bearing the microencapsulated colorless precursor on its reverseside causing the affected microcapsules to rupture thus allowing thesolution of the colorless precursor held by said microcapsules to flowinto contact with the color developing substance on the receiving sheetwhereupon a deep blue-colored image promptly formed. The developed imageexhibited good lightfastness when exposed to daylight or to a daylightfluorescent lamp for extended periods.

When evaluated in a duplicating system prepared and tested as describedabove, the product of Example 29,3-(4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-ethoxycarbonylphthalide,produced a blue-colored developed image; the product of Example 34,3-(2-methyl-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-ethoxycarbonylphthalide,produced a turquoise-colored developed image; the product of Example39B, 3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide,produced a deep red-colored developed image; the product of Example 2B,3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-4,5,6,7-tetrachlorophthalide,produced a deep grape-colored developed image; the product of Example3B,3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-6-nitrophthalide,produced a blue-black-colored image.

EXAMPLE 115

When evaluated in a carbonless duplicating system by proceeding in amanner similar to that described in Example 114 above, except that soyoil was used in places of alkylated biphenyls, the product of Example20,3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-n-octyloxycarbonylphthalide,produced a grape-colored developed image; and the product of Example 46,3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-n-octyloxycarbonylphthalide,produced a deep red-colored developed image.

EXAMPLE 116

Following a procedure similar to that described in Example 114 but usingkerosene instead of alkylated biphenyls for evaluation in a carbonlessduplicating system, the product of Example 26,3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-hexadecyloxycarbonylphthalide,produced a deep blue-colored developed image.

EXAMPLE 117

The utility of the phthalides of Formulas I to IV whose preparations aredescribed in the foregoing examples as color forming components inthermal marking systems is illustrated by the incorporation and testingof the compound of Example 22B,3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalidein a thermal sensitive marking paper. The test paper was prepared by aprocedure similar to that described in U.S. Pat. No. 3,539,375.

A. A mixture of 2.0 g of3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide,8.6 g of a ten percent aqueous solution of polyvinyl alcohol(approximately 99 percent hydrolyzed), 3.7 g of water and 31.6 g of 1/16inch diameter zirconium grinding beads was charged into a containerwhich was placed in a mechanical shaker. Shaking was effected for onehour. The zirconium beads were then removed by straining the mixturethrought a No. 40 sieve.

B. Similarly, a mixture of 9.8 g of 4,4'-isopropylidine diphenol(Bisphenol A), 42.0 g of a ten percent aqueous polyvinyl alcoholsolution (approximately 99 percent hydrolyzed), 18.2 g of water and221.2 g of 1/16 inch diameter zirconium grinding beads was charged intoa container which was placed in a mechanical shaker. After shaking waseffected for one hour, the zirconium beads were removed by strainingthrought a No. 40 sieve.

C. A coating composition was prepared by mixing 2.1 g of the slurry fromA and 47.9 g of the slurry from B. The mixture was then uniformly coatedon sheets of paper at thicknesses of approximately 0.003 inch and thecoated sheets air-dried. The coated paper was tested by tracing a designon the coated side of the paper placed on a smooth flat surface with astylus heated to approximately 125° C. A deep blue-colored imagecorresponding to the traced design promptly developed.

When evaluated in thermal marking paper prepared and tested as describedabove, the product of Example 39B,3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide,produced a violet-colored image; the product of Example 21,3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-phenylmethoxycarbonylphthalide,produced a grape-colored image; the product of Example 28B,3-(4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide,produced a blue-colored image; the product of Example 33B,3-(2-methyl-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide,produced a turquoise-colored image; the product of Example 1B,3-[2,4-bis(diethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)phthalide,produced a blue-black-colored image; the product of Example 1C,3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)phthalide,produced a grape-colored image; the product of Example 2B,3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-4,5,6,7-tetrachlorophthalide,produced a deep grape-colored developed image; the product of Example3B,3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-6-nitrophthalide,produced a blue-black-colored image.

We claim:
 1. A pressure-sensitive carbonless duplicating system orthermal marking system containing as a color-forming substance a3-X-3-Z-4-R°-5-R¹ -6-R² -7-R³ -phthalide of the formula ##STR29##wherein: R°, R¹, R² and R³ each represent hydrogen or halo or when R°,R³ and one of R¹ and R² are each hydrogen, the other of R¹ and R²represents ##STR30## in which B represents -OY or ##STR31## wherein Y ishydrogen, an alkali metal cation, an ammonium cation, a C₁ to C₁₈ mono-,di- or trialkylammonium cation, C₁ to C₁₈ alkyl, C₂ to C₁₈ alkenyl,benzyl or benzyl substituted in the benzene ring thereof by C₁ to C₁₂alkyl, halo or C₁ to C₈ alkoxy;Y' is hydrogen or C₁ to C₁₈ alkyl; Y" ishydrogen, C₁ to C₁₈ alkyl or C₄ to C₁₂ N,N-dialkylaminoalkyl; Xrepresents a monovalent moiety selected from the class having theformulas ##STR32## Z represents a monovalent moiety selected from theclass having the formulas ##STR33## in which R represents non-tertiaryC₁ to C₄ alkyl, benzyl or benzyl substituted in the benzene ring by oneor two of halo or C₁ to C₃ alkyl, R⁴ represents acetamido, dialkylaminoin which alkyl is non-tertiary C₁ to C₄ alkyl, and when one of R¹ or R²represents said ##STR34## R⁴ further represents hydrogen, C₁ to C₃alkyl, C₁ to C₄ alkoxy or halo, R⁵ and R^(5') represent hydrogen, C₁ toC₃ alkyl or phenyl, R⁶ and R^(6') represent hydrogen, C₁ to C₁₈ alkyl,C₂ to C₄ alkenyl, benzyl or benzyl substituted in the benzene ring byone or two of halo or C₁ to C₃ alkyl, R⁷ and R⁸ represent hydrogen, C₁to C₃ alkyl or phenyl, and Y¹ and Y^(1') represent one or two ofhydrogen, C₁ to C₃ alkyl, C₁ to C₃ alkoxy, halo or nitrowith theprovisos (i) that X and Z can both simultaneously represent monovalentindolyl moieties only when one of R¹ and R² represents said ##STR35##and (ii) X represents a pyrrolyl or a carbazolyl moiety only when Zrepresents a 2-R⁴ -4-N(R)₂ -phenyl moiety.
 2. A pressure-sensitivecarbonless duplicating system according to claim 1 comprising a supportsheet coated on one side with a layer of pressure-rupturablemicrocapsules containing a liquid solution of the color-formingsubstance.
 3. A thermal marking system according to claim 1 comprising asupport sheet coated on one side with a layer containing a mixture ofthe color-forming substance and an acidic developer arranged such thatapplication of heat will produce a mark-forming reaction between thecolor-forming substance and the acidic developer.
 4. A hectographiccopying system comprising a support sheet coated on one side with alayer containing a color-forming substance comprising a compoundaccording to claim 1 wherein R°, R³ and one of R¹ and R² are eachhydrogen, the other of R¹ and R² represents ##STR36## wherein Y is analkali metal cation, an ammonium cation or a C₁ to C₁₈ mono-, di- ortrialkylammonium cation.
 5. A pressure-sensitive carbonless duplicatingsystem or thermal marking system according to claim 1 containing as thecolor-forming substance a 3-[2-R⁴ -4-N(R)₂ -phenyl]-3-[(1-R⁶ -2-R⁵-5/6-Y¹)-3-indolyl]-4-R°-5-R¹ -6-R² -7-R³ -phthalide wherein R, R°, R¹,R², R³, R⁴, R⁵, R⁶ and Y¹ have the same respective meanings given inclaim
 1. 6. A pressure-sensitive carbonless duplicating system orthermal marking system according to claim 5 containing as acolor-forming substance3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methy-3-indolyl)phthalide.7. A pressure-sensitive carbonless duplicating system or thermal markingsystem according to claim 5 containing as a color-forming substance3-[2,4-bis(diethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)phthalide.8. A pressure-sensitive carbonless duplicating system or thermal markingsystem according to claim 5 containing as a color-forming substance3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-4,5,6,7-tetrachlorophthalide.9. A pressure-sensitive carbonless duplicating system or thermal markingsystem according to claim 5 containing as a color-forming substance3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-ethoxycarbonylphthalide.10. A pressure-sensitive carbonless duplicating system or thermalmarking system according to claim 5 containing as a color-formingsubstance3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-hexadecyloxycarbonylphthalide.11. A pressure-sensitive carbonless duplicating system or thermalmarking system according to claim 1 containing as the color-formingsubstance a 3-[(1-R⁶ -2-R⁵ -5/6-Y¹)-3-indolyl]-3-[(1-R^(6') -2-R^(5')-5/6-Y^(1') -3-indolyl]-4-R°-5-R¹ -6-R² -7-R³ -phthalide wherein R°, R¹,R², R³, R⁵, R⁶, R^(5'), R^(6'), Y¹ and Y^(1') have the same respectivemeanings given in claim
 51. 12. A pressure-sensitive carbonlessduplicating system or thermal marking system according to claim 11containing as the color-forming substance3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide.
 13. Apressure-sensitive carbonless duplicating system or thermal markingsystem according to claim 11 containing as the color-forming substance3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-n-octyloxycarbonylphthalide. 14.A pressure-sensitive carbonless duplicating system or thermal markingsystem according to claim 11 containing as the color-forming substance3,3-bis(1-ethyl-2-methyl-3-indolyl)-5/6-n-hexadecyloxycarbonylphthalide.15. A pressure-sensitive carbonless duplicating system or thermalmarking system containing as a color-forming substance a3-X-3-Z-4-R°-5-R¹ -6-R² -7-R³ -phthalide of the formula ##STR37##wherein: R°, R³ and one of R¹ and R² are each hydrogen, the other of R¹and R² represents nitro, amino, acetamido or dialkylamino wherein alkylis non-tertiary C₁ to C₄ alkyl;X represents a monovalent moiety selectedfrom the class having the formulas ##STR38## Z represents a monovalentmoiety having the formula ##STR39## in which R represents non-tertiaryC₁ to C₄ alkyl, benzyl or benzyl substituted in the benzene ring by oneor two of halo or C₁ to C₃ alkyl, R⁴ represents dialkylamino in whichalkyl is non-tertiary C₁ to C₄ alkyl, R⁵ represents hydrogen, C₁ to C₃alkyl or phenyl, R⁶ represents hydrogen, C₁ to C₁₈ alkyl, C₂ to C₄alkenyl, benzyl or benzyl substituted in the benzene ring by one or twoof halo or C₁ to C₃ alkyl, R⁷ and R⁸ represent hydrogen, C₁ to C₃ alkylor phenyl, and Y¹ represents one or two of hydrogen, C₁ to C₃ alkyl, C₁to C₃ alkoxy, halo or nitro.